CN205631608U - Power storage device is with adorning component outward and having used this outer power storage device who adorns component - Google Patents

Power storage device is with adorning component outward and having used this outer power storage device who adorns component Download PDF

Info

Publication number
CN205631608U
CN205631608U CN201620159207.8U CN201620159207U CN205631608U CN 205631608 U CN205631608 U CN 205631608U CN 201620159207 U CN201620159207 U CN 201620159207U CN 205631608 U CN205631608 U CN 205631608U
Authority
CN
China
Prior art keywords
layer
exterior member
storage device
substrate layer
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201620159207.8U
Other languages
Chinese (zh)
Inventor
伊集院涉
佐佐木聪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toppan Inc
Original Assignee
Toppan Printing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2015041274A external-priority patent/JP6819029B2/en
Priority claimed from JP2015041271A external-priority patent/JP6596844B2/en
Application filed by Toppan Printing Co Ltd filed Critical Toppan Printing Co Ltd
Application granted granted Critical
Publication of CN205631608U publication Critical patent/CN205631608U/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H01G11/82—Fixing or assembling a capacitive element in a housing, e.g. mounting electrodes, current collectors or terminals in containers or encapsulations
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/145—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against corrosion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
    • H01M50/55—Terminals characterised by the disposition of the terminals on the cells on the same side of the cell
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/16—Capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Laminated Bodies (AREA)

Abstract

The utility model relates to a power storage device is with adorning component outward and having used this outer power storage device who adorns component. Above -mentioned power storage device has to major general's substrate layer, adhesive linkage, metal foil layer, prevents that corrosion treatment layer, sealed adhesive linkage and sealing layer stack gradually the structure that forms with adorning the member outward. Above -mentioned substrate layer for be less than by 95 DEG C of hot water shrinkage factors 5% and 180 DEG C of heat shrinkage be layer that 4~16% polyamide membrane constitutes, or by 95 DEG C of hot water shrinkage factors be less than 5% and 180 DEG C of heat shrinkage be 10~25% polyester film component layer. Above -mentioned power storage device is with adorning outward that the component can improve the deep -draw formability and maintain the adaptation between substrate layer and the metal foil layer during with the use when battery manufacturing.

Description

Electrical storage device exterior member and the electrical storage device employing this exterior member
Technical field
This utility model relates to electrical storage device exterior member and employs the electrical storage device of this exterior member.
Background technology
As electrical storage device, the secondary cell such as the most known lithium ion battery, Ni-MH battery and lead battery And the electrochemical capacitor such as double layer capacitor.Miniaturization or the limit of installation space due to portable equipment System etc., it is desirable to the further miniaturization of electrical storage device, the lithium ion battery that energy density is high receives publicity. As the exterior member used in lithium ion battery, employed metal tank in the past, but the most gradually made High with light weight, thermal diffusivity, can be with the multilayer film of low-cost production.
For above-mentioned multilayer film being used for the lithium ion battery of exterior member, in order to prevent moisture from internally soaking Enter, have employed by the exterior member comprising aluminium foil layer by battery content (positive pole, barrier film, negative pole, Electrolyte etc.) composition that covers.The lithium ion battery that have employed such composition is referred to as the lithium of aluminium lamination mould assembly Ion battery.
The lithium ion battery of aluminium lamination mould assembly is the most known to be had: pass through cold forming in a part for exterior member Form recess, in this recess, accommodate battery content, by the residual fraction turnover of exterior member and by limit The pattern pressing type lithium ion battery that edge portion carries out sealing by heat-sealing and obtains is (referring for example to Japanese Unexamined Patent Publication 2013-101765 publication).For such lithium ion battery, more make the recess formed by cold forming Deepen, more can accommodate more battery content, therefore, it is possible to improve energy density further.
But, if carried out conventional electrical storage device exterior member being formed the deep-draw molding of deep recess, The most sometimes there is adhesive linkage and the fracture of metal foil layer.Therefore, for exterior member, it is desirable to improve Deep-draw mouldability.
It addition, in the manufacturing process of exterior member, it is sometimes desirable to make multiple layer stackup lamination procedure and By the bonding agent drying process of layers cementing.But, due to heating during lamination or time dry, base sometimes Sheet material layers generation thermal contraction, the adaptation between substrate layer and metal foil layer reduces.By thermally-induced substrate layer And under the reduction of the adaptation between metal foil layer not only hot environment when lamination or time dry easily Occur, and in the hot water or be also susceptible under hot and humid environment.
And then, in the manufacturing process of battery, the electrolyte in battery spills to outside sometimes.Now, The electrolyte spilt is attached to the battery of its periphery, and the battery making its periphery due to the electrolyte that spills is sudden and violent It is exposed to electrolyte atmosphere, the most sometimes metal foil layer is corroded.It is exposed to electrolysis so making exterior member In the case of liquid, the adaptation between substrate layer and metal foil layer is also possible to reduce.
And, when exterior member is taken care of for a long time, result from substrate layer as described above and metal foil layer it Between the reduction of adaptation, sometimes peeling-off between substrate layer and metal foil layer.Therefore, for outward Even if dress component requires be exposed to heat (high temperature, hot water and hot and humid) and/or the situation of electrolyte Under also be able to suppress chronically excellent adaptation peeling-off between substrate layer and metal foil layer.
Utility model content
This utility model completes in view of the foregoing, its object is to offer and can improve deep-draw Type and maintain adaptation between substrate layer and metal foil layer when the manufacture of battery and when using Electrical storage device exterior member and the electrical storage device employing this exterior member.
To achieve these goals, this utility model provides a kind of electrical storage device exterior member, and it has Depend on to major general's substrate layer, adhesive linkage, metal foil layer, corrosion-proof layer, sealing adhesive linkage and sealant The secondary structure being laminated.
According to above-mentioned electrical storage device exterior member, above-mentioned substrate layer is preferably by 95 DEG C of hot water shrinkages Less than 5% and 180 DEG C of percent thermal shrinkages are 4～the layer that constitutes of polyamide membrane of 16% or by 95 DEG C of heat Water shrinkage factor is less than 5% and the layer that constitutes of polyester film that 180 DEG C of percent thermal shrinkages are 10～25%.
According to above-mentioned electrical storage device exterior member, by possessing by 95 DEG C of hot water shrinkages and 180 DEG C of heat Both shrinkage factors be above-mentioned specific in the range of polyamide membrane or the substrate layer that constitutes of polyester film, thus While can improving making deep-draw mouldability, when the manufacture of battery and when using, maintain substrate layer and gold Belong to the adaptation between layers of foil.Therefore, according to above-mentioned electrical storage device exterior member, it is possible to do not sending out Form depth is improved, even if be exposed to heat simultaneously in the case of the fracture of raw adhesive linkage and metal foil layer It also is able to suppress chronically substrate layer in the case of (high temperature, hot water and hot and humid) and/or electrolyte And it is peeling-off between metal foil layer.
Above-mentioned electrical storage device exterior member is preferably also equipped with between above-mentioned substrate layer and above-mentioned adhesive linkage Easy the to be bonding process layer arranged.Thereby, it is possible to improve the adaptation between substrate layer and adhesive linkage further, Deep-draw mouldability can be improved further simultaneously.
In above-mentioned electrical storage device exterior member, the most above-mentioned easy bonding process layer is to comprise selected from polyester tree Among fat, acrylic resin, polyurethane resin, epoxy resin and acrylic graft polyester resin The layer of at least one resin.Thereby, it is possible to improve the adaptation between substrate layer and adhesive linkage further, Deep-draw mouldability can be improved further simultaneously.
In above-mentioned electrical storage device exterior member, the most above-mentioned corrosion-proof layer is arranged on above-mentioned metal On the two sides of layers of foil.Thereby, it is possible to improve the adaptation between substrate layer and metal foil layer further.
In above-mentioned electrical storage device exterior member, the most above-mentioned corrosion-proof layer comprises: rare earth element Oxide；And phosphoric acid or phosphate.Thereby, it is possible to improve further between substrate layer and metal foil layer Adaptation.
In above-mentioned electrical storage device exterior member, the most above-mentioned rare earth element oxide is cerium oxide.By This, it is possible to improve the adaptation between substrate layer and metal foil layer further.
This utility model additionally provides electrical storage device, and it possesses: comprise the battery unit of electrode；From above-mentioned The lead-in wire that electrode extends out；With the container of the above-mentioned battery unit of receiving, wherein, said vesse is by above-mentioned Electrical storage device exterior member of the present utility model is formed in the way of making described sealant become inner side.Should In electrical storage device, as the container of receiving battery unit, owing to using above-mentioned electric power storage of the present utility model dress Put by exterior member, therefore, it is possible to do not produce formed in a reservoir in the case of fracture waits deep recessed Portion.Even if it addition, above-mentioned electrical storage device thermally and/or electrically solves in the case of liquid exterior member being exposed to, It also is able to suppress peeling-off between substrate layer and metal foil layer chronically.
According to this utility model, using the teaching of the invention it is possible to provide can improve deep-draw mouldability and when the manufacture of battery and Maintain the electrical storage device exterior member of the adaptation between substrate layer and metal foil layer during use and make With the electrical storage device of this exterior member.
Accompanying drawing explanation
Fig. 1 is the general profile chart of the electrical storage device exterior member of an embodiment of the present utility model.
Fig. 2 is to represent that the electrical storage device exterior member using an embodiment of the present utility model obtains The figure of pattern pressing type exterior member, (a) is its axonometric chart, and (b) is along the pattern pressing type shown in (a) The longitudinal section of the b-b line of exterior member.
Fig. 3 is to represent that the electrical storage device exterior member using an embodiment of the present utility model manufactures The axonometric chart of the operation of secondary cell, (a) represents the state preparing electrical storage device exterior member, (b) Represent and prepared the electrical storage device exterior member and the state of battery unit, (c) that are processed to pattern pressing type Represent that (d) represents by the part turnover of electrical storage device exterior member and by end state after melted State after the both sides of the part turned down are turned down upward.
[explanation of reference]
1 battery unit, 2 lead-in wires, 10 exterior member (electrical storage device exterior member), 11 substrate layers, 12 easy bonding process layers, 13 adhesive linkages, 14 metal foil layers, 15a, 15b corrosion-proof layer, 16 seal adhesive linkages, 17 sealants, 30 pattern pressing type exterior member, 32 processing and forming regions (recess), 34 caps, 40 secondary cells.
Detailed description of the invention
Preferred embodiment it is described in detail of the present utility model referring to the drawings.Need Bright, in accompanying drawing, at same or considerable part labelling same symbol, the repetitive description thereof will be omitted.
[electrical storage device exterior member]
Fig. 1 is the embodiment showing schematically electrical storage device exterior member of the present utility model Sectional view.As illustrated in figure 1, the exterior member (electrical storage device exterior member) of present embodiment 10 is by substrate layer 11, at easy the to be bonding process layer 12 of the one side side of this substrate layer 11 setting, at this The adhesive linkage 13 arranged with the opposition side of substrate layer 11 of easy bonding process layer 12, at this adhesive linkage 13 Arrange with the opposition side of easy bonding process layer 12 and have on two sides corrosion-proof layer 15a, The metal foil layer 14 of 15b, the sealing arranged in the opposition side with adhesive linkage 13 of this metal foil layer 14 are glued Connect layer 16 and the sealant 17 arranged in the opposition side with metal foil layer 14 of this sealing adhesive linkage 16 depends on The duplexer of secondary stacking.Here, corrosion-proof layer 15a is arranged on the adhesive linkage 13 of metal foil layer 14 The face of side, corrosion-proof layer 15b is arranged on the face sealing adhesive linkage 16 side of metal foil layer 14.Outward The substrate layer 11 of dress component 10 is outermost layer, and sealant 17 is innermost layer.That is, make substrate layer 11 to The outer side of electrical storage device, make sealant 17 use exterior member towards the private side of electrical storage device 10.Hereinafter each layer is illustrated.
(substrate layer 11)
Substrate layer 11 be for by manufacture electrical storage device time pressurized heat fusion process described later in heat-resisting Property and the electrolyte resistance of electrolyte for spilling from other electrical storage device give exterior member 10, The layer of the generation of generable pin hole when suppression processing or circulation.It addition, substrate layer 11 is by 95 DEG C of heat Water shrinkage factor less than 5% and 180 DEG C of percent thermal shrinkages be 4～the layer that constitutes of polyamide membrane of 16% or by 95 DEG C of hot water shrinkages are less than 5% and the layer that constitutes of polyester film that 180 DEG C of percent thermal shrinkages are 10～25%.
Here, 95 DEG C of hot water shrinkages are the value using following method to measure.That is, 95 DEG C hot water shrink Rate is to calculate as follows: substrate layer 11 is cut into the size of vertical 10cm × horizontal 10cm Coupons impregnates 30 minutes in the hot water of 95 DEG C, based on following formula (I) obtain coupons longitudinal direction and The laterally size changing rate before and after the dipping on (2 orthogonal directions), as the size in 2 directions The meansigma methods of rate of change calculates.It should be noted that make the vertical and horizontal of coupons respectively with base material The MD direction (mechanical transmission direction) of layer base material and TD direction (vertical direction in MD direction) Cause.That is, in the case of substrate layer 11 is made up of biaxially-stretched film, the vertical and horizontal of coupons are respectively Consistent with any one direction of the 2 of film draw directions.
It addition, 180 DEG C of percent thermal shrinkages are to calculate as follows: substrate layer 11 is cut into vertical The coupons of the size of 10cm × horizontal 10cm heats 30 minutes in the baking oven of 180 DEG C, based on following Formula (I) obtains the size before and after the heating on the vertical and horizontal (2 orthogonal directions) of coupons Rate of change, the meansigma methods as the size changing rate in 2 directions calculates.It should be noted that sample The situation of the vertical and horizontal of sheet and 95 DEG C of hot water shrinkages is same.
Size changing rate (%)={ (X-Y)/X} × 100 (I)
[X: size before the heat treated before impregnation process or in baking oven, Y in the hot water: at hot water The size after heat treated after middle impregnation process or in baking oven]
Below by by 95 DEG C of hot water shrinkages less than 5% and polyamide that 180 DEG C of percent thermal shrinkages are 4～16% The substrate layer 11 that film is constituted is referred to as " substrate layer 11a ", will be by 95 DEG C of hot water shrinkages less than 5% and 180 DEG C percent thermal shrinkage be 10～25% the substrate layer 11 that constitutes of polyester film be referred to as " substrate layer 11b ", to it Illustrate respectively.
(substrate layer 11a)
About exterior member 10, by constituting 95 DEG C of hot water shrinkages of the polyamide membrane of substrate layer 11a Less than 5%, thermally and/or electrically solve in the case of liquid being exposed to, it is possible to chronically suppression substrate layer 11a with Between metal foil layer 14 peeling-off.It addition, from can suppress the most chronically substrate layer 11a with Peeling-off consideration between metal foil layer 14,95 DEG C of hot water shrinkages of polyamide membrane be preferably 4% with Under.It addition, from the same viewpoint, 95 DEG C of hot water shrinkages of polyamide membrane are preferably more than 0%.
It addition, about exterior member 10, received by the 180 DEG C of heat constituting the polyamide membrane of substrate layer 11a Shrinkage is more than 4%, it is possible to increase deep-draw mouldability, it is possible to adhesive linkage 13 and metal forming are not occurring Improving in the case of the fracture of layer 14 can the form depth of deep-draw molding.Additionally, it is deep from improving further From the viewpoint of rushing mouldability, 180 DEG C of percent thermal shrinkages of polyamide membrane are preferably more than 5%.The opposing party Face, about exterior member 10, by constituting 180 DEG C of percent thermal shrinkages of the polyamide membrane of substrate layer 11a be Less than 16%, thermally and/or electrically solve in the case of liquid being exposed to, it is possible to suppression substrate layer 11a chronically And it is peeling-off between metal foil layer 14.It addition, be prevented from due to thermally-induced by apply when manufacturing Thermal contraction and produce hot fold.
From the viewpoint of can obtaining more excellent deep-draw mouldability, substrate layer 11a is preferably and is drawn by twin shaft Stretch the layer that polyamide membrane is constituted.
As the polyamide of composition biaxial stretching polyamide film, include, for example out nylon 6, nylon 6,6, nylon 6 and the copolymer of nylon 6,6, nylon 6,10, poly-m-xylylene adipamide (MXD6), nylon 11, nylon 12 etc..Among these, from thermostability, pierce through intensity and impact strong From the viewpoint of degree excellence, preferably nylon 6 (ONy).
As the drawing process of biaxially-stretched film, include, for example out gradually biaxial stretching process, tubular type twin shaft Pulling method, simultaneously biaxial stretching process etc..From the viewpoint of can obtaining more excellent deep-draw mouldability, double Axle stretched film is preferably and uses tubular type biaxial stretching process to stretch and winner.
The thickness of substrate layer 11a is preferably 6～40 μm, more preferably 10～30 μm.Pass through substrate layer The thickness of 11a is more than 6 μm, thus there is the resistance to pin that can improve electrical storage device exterior member 10 Permeability and the tendency of insulating properties.If the thickness of substrate layer 11a is more than 40 μm, then electrical storage device is with outward The gross thickness of dress component 10 becomes big, and the capacitance of battery sometimes must be made to diminish, the most preferred.
(substrate layer 11b)
About exterior member 10, low by constituting 95 DEG C of hot water shrinkages of the polyester film of substrate layer 11b In 5%, thermally and/or electrically solve in the case of liquid being exposed to, it is possible to suppress chronically substrate layer 11b with Between metal foil layer 14 peeling-off.It addition, from can suppress to longer-term at substrate layer 11b and gold Belonging to 95 DEG C of hot water shrinkages of peeling-off consideration, preferably polyester film between layers of foil 14 is less than 4%. It addition, from the same viewpoint, preferably 95 DEG C of hot water shrinkages of polyester film are more than 0%.
It addition, about exterior member 10, by constituting 180 DEG C of thermal contractions of the polyester film of substrate layer 11b Rate is more than 10%, it is possible to increase deep-draw mouldability, it is possible to do not producing adhesive linkage 13 and metal forming Improving in the case of the fracture of layer 14 can the form depth of deep-draw molding.On the other hand, about exterior structure Part 10, is less than 25% by constituting 180 DEG C of percent thermal shrinkages of the polyester film of substrate layer 11b, is exposing In the case of thermally and/or electrically solving liquid, it is possible to chronically between suppression substrate layer 11b and metal foil layer 14 Peeling-off.It addition, be prevented from owing to being produced hot pleat by the thermally-induced thermal contraction applied when manufacturing Wrinkle.
From the viewpoint of can obtaining more excellent deep-draw mouldability, substrate layer 11b is preferably and is drawn by twin shaft Stretch the layer that polyester film is constituted.
As the polyester resin of composition biaxially oriented polyester film, such as poly terephthalic acid second two can be listed Alcohol ester, polybutylene terephthalate (PBT), PEN, PBN, Copolyester etc..
As the drawing process of biaxially-stretched film, include, for example out gradually biaxial stretching process, tubular type twin shaft Pulling method, simultaneously biaxial stretching process etc..From the viewpoint of can obtaining more excellent deep-draw mouldability, double Axle stretched film preferably employs tubular type biaxial stretching process and simultaneously biaxial stretching process stretching and winner.
The thickness of substrate layer 11b is preferably 6～40 μm, more preferably 10～30 μm.Pass through substrate layer The thickness of 11b is more than 6 μm, there is the pinhole resistance that can improve electrical storage device exterior member 10 Tendency with insulating properties.If the thickness of substrate layer 11b is more than 40 μm, electrical storage device exterior member The gross thickness of 10 becomes big, sometimes must reduce the capacitance of battery, the most preferred.
(easy bonding process layer 12)
Easy bonding process layer 12 is arranged on the one side side of substrate layer 11, is arranged in substrate layer 11 with viscous Connect between layer 13.Easy bonding process layer 12 is close for improve between substrate layer 11 and adhesive linkage 13 Conjunction property and then the layer of the adaptation between raising substrate layer 11 and metal foil layer 14.Electrical storage device is with outward In dress component 10, it is possible to be not provided with easy bonding process layer 12.In this case, in order to improve substrate layer Adaptation between 11 and adhesive linkage 13, so improve between substrate layer 11 and metal foil layer 14 close Conjunction property, it is also possible to the face of adhesive linkage 13 side of substrate layer 11 is carried out sided corona treatment.
Easy bonding process layer 12 preferably comprises selected from polyester resin, acrylic resin, polyurethane tree The layer of at least one resin among fat, epoxy resin and acrylic graft polyester resin.This is the most bonding Processing layer 12 such as can be by being coated with selected from polyester resin, acrylic acid in the one side of substrate layer 11 It it is at least one tree among resin, polyurethane resin, epoxy resin and acrylic graft polyester resin Fat is formed as the smears of main constituent.
＜ polyester resin ＞
As polyester resin, from the standpoint of cementability, preferably import copolymer composition and make vitrification turn The copolyester that temperature reduces.From the standpoint of coating, copolyester preferably have water solublity or Water dispersible.As such copolyester, it is preferably used and is bonded with selected from sulfonic group or its alkali metal salt The copolyester (hereinafter referred to as " containing sulfonic copolyester ") of at least one group among base.
Here, refer among sulfonic group or its alkali metal alkali extremely containing sulfonic copolyester The polyester that few a kind of group is bonded with the part of dicarboxylic acid component or diol component, the most especially Be, preferably with respect to all acid composition with the ratio of 2～10 moles of % use containing selected from sulfonic group or its The aromatic dicarboxylic acid composition of at least one group among alkali metal alkali and the copolyester prepared.
As the example of such dicarboxylic acids, preferably 5-sodiosulfoisophthalic acid.In this case, make For other dicarboxylic acid component, p-phthalic acid, M-phthalic acid, phthalic acid, right can be listed -beta-hydroxy ethoxybenzoic acid, NDA, 4,4 '-dicarboxylate biphenyl, 4,4 '-dicarboxyl Base benzophenone, double (4-carboxyl phenyl) ethane, adipic acid, decanedioic acid, hexamethylene-Isosorbide-5-Nitrae-diformazan Acid etc..
As for manufacturing the diol component containing sulfonic copolyester, mainly make spent glycol, this Outward, it is possible to use propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, bisphenol-A Ethylene oxide adduct, Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol etc..The most especially, if Make spent glycol, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol etc. as altogether It is polymerized to point, is then preferred at the aspect improved with the compatibility of poly styrene sulfonate.
It addition, as polyester resin, modified polyesters can be used, such as with polyester, carbamic acid The block copolymer of the modification such as ester, epoxy, graft copolymer etc..In present embodiment, in order to improve easily Adaptation between bonding process layer 12 and substrate layer 11 and adhesive linkage 13, at easy bonding process layer 12 In can contain the resin beyond polyester resin further.As such resin, the most poly-ammonia can be listed Ester resin, acrylic resin etc..
＜ acrylic resin ＞
As the monomer component of composition acrylic resin, such as, can use alkyl acrylate, methyl Alkyl acrylate (as alkyl, can list methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, Isobutyl group, the tert-butyl group, 2-ethylhexyl, lauryl, stearyl, cyclohexyl, phenyl, benzyl, benzene Base ethyl etc.)；Acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxyl third The monomer containing hydroxyl such as ester, methacrylic acid 2-hydroxy propyl ester；Acrylamide, Methacrylamide, N methacrylamide, N-methyl methacrylamide, N hydroxymethyl acrylamide, N-methylol first Base acrylamide, N, N-dihydroxymethyl acrylamide, N-methoxy acrylamide, N-methoxyl group The monomer containing acylamino-such as methyl methacrylamide, N phenyl acrylamide；Acrylic acid N, N- The monomer containing amino such as diethylamino ethyl ester, DEAEMA；Third The monomer containing epoxy radicals such as olefin(e) acid ethylene oxidic ester, glycidyl methacrylate；Acrylic acid, first Base acrylic acid and their salt (lithium salts, sodium salt, potassium salt etc.) etc. are containing carboxyl or the monomer etc. of its salt. These can be used alone a kind, it is possible to use two or more carries out copolymerization.And then, these unit can be with Other monomers other than the above are also used.
As other monomer, such as, can use: allyl glycidyl ether etc. are containing epoxy radicals Monomer；Styrene sulfonic acid, vinyl sulfonic acid and their salt (lithium salts, sodium salt, potassium salt, ammonium salt etc.) Deng containing sulfonic group or the monomer of its salt；.beta.-methylacrylic acid, itaconic acid, maleic acid, fumaric acid and their salt (lithium salts, sodium salt, potassium salt, ammonium salt etc.) etc. are containing carboxyl or the monomer of its salt；Maleic anhydride, clothing health The monomer containing anhydride such as anhydride；Vinyl isocyanate, allyl isocyanate, styrene, vinyl first Base ether, EVE, vinyl trialkyl oxysilane, maleic acid alkyl monoester, fumaric acid alkyl Monoesters, acrylonitrile, methacrylonitrile, itaconic acid alkyl monoester, vinylidene chloride, vinylacetate, chlorine Ethylene etc..It addition, as acrylic resin, modified acroleic acid based copolymer can be used, such as with poly- The block copolymer of the modification such as ester, carbamate, epoxy, graft copolymer etc..
The glass transition temperature (Tg) of the acrylic resin used in present embodiment be there is no spy Do not limit, but preferably 0～90 DEG C, more preferably 10～80 DEG C.If Tg is low, high temperature the most sometimes Adaptation under high humidity reduces, if Tg is high, the most sometimes cracks, therefore from suppression when stretching From the viewpoint of these shortcomings, the Tg of acrylic resin is preferably in above-mentioned scope.
It addition, the weight average molecular weight of the acrylic resin used in present embodiment is preferably 100,000 Above, more preferably more than 300,000.If weight average molecular weight is low, humidity resistance reduces the most sometimes.This In embodiment, close in order to improve between easy bonding process layer 12 and substrate layer 11 and adhesive linkage 13 Conjunction property, it is possible to so that the process layer 12 that connects easy to stick contains the resin beyond acrylic resin further.Make For such resin, include, for example out polyester resin, polyurethane resin etc..
＜ polyurethane resin ＞
As polyurethane resin, preferably aqueous polyurethane resin.As aqueous polyurethane resin, from particle diameter Little, have good stability from the standpoint of, preferably be selected from oil-in-water type.The particle diameter of aqueous polyurethane resin is set as 10～about 100nm.Preferably its vitrification of aqueous polyurethane resin used in present embodiment Transition temperature (Tg) is 40 DEG C～150 DEG C.If Tg is more than 40 DEG C, then existing can be in coating After be adequately suppressed the tendency that adhesion occurs when batching as web-like.On the other hand, if with coating after dry Dry temperature is compared, and Tg is too high, then be difficult to be formed uniform film, and therefore Tg is preferably less than 150 DEG C.
It addition, in present embodiment, cross-linking agent can be used together with aqueous polyurethane resin.As water It is the cross-linking agent of polyurethane, it is possible to use the general water-soluble cross-linkers such as soluble epoxide compound.Water Dissolubility epoxide is the dissolubility having in water, the compound with the epoxy radicals of more than 2. As soluble epoxide compound, include, for example out by ethylene glycol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., poly-second Glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, BDO, 1,6-oneself two The glycols such as alcohol, neopentyl glycol 1 mole and chloropropylene oxide 2 moles etherificate and obtain polyepoxy compound, And by the omega-dicarboxylic acids 1 mole such as phthalic acid, p-phthalic acid, adipic acid, oxalic acid and table chlorine The di-epoxy compounds etc. that alcohol 2 moles is esterified and obtains.But, soluble epoxide compound is not limited to These.
These water-soluble cross-linkers and aqueous polyurethane resin crosslinks, improve the resistance to water of film, solvent resistant Property, it helps the adaptation between easy bonding process layer 12 and substrate layer 11 and adhesive linkage 13 improves. In present embodiment, in order to improve between easy bonding process layer 12 and substrate layer 11 and adhesive linkage 13 Adaptation, can contain the resin beyond polyurethane resin further.As such resin, such as, can arrange Enumerate polyester resin, acrylic resin etc..
It addition, easy bonding process layer 12 can be to comprise such as the above-mentioned resin of main constituent and many The mode of the firming agent such as functional isocyanate, multifunctional glycidyl compound, melamine based compound is come Constitute.So, by comprising the above-mentioned resin as main constituent and polyfunctional isocyanate, multifunctional The firming agent such as glycidyl compound, melamine based compound, introduce cross-linked structure and become possibility, therefore Strong easy to be bonding process layer 12 can be constituted.
The smears used to form easy bonding process layer 12 can be solvent system, it is also possible to be water System.The molecular weight of the decentralized (dispersion) employing the host of water system is big, and intermolecular cohesiveness improves, Thus be effective to the adaptation between easy bonding process layer 12 and substrate layer 11 and adhesive linkage 13.
The thickness of easy bonding process layer 12 is preferably 0.02～0.5 μm, more preferably 0.04～0.3 μm. If the thickness of easy bonding process layer 12 is more than 0.02 μm, then there is following tendency: easily formed Homogeneous easy to be bonding process layer 12, can obtain more fully easily adhesive effect.On the other hand, by easily The thickness of bonding process layer 12 is below 0.5 μm, exists and can improve the deep of exterior member 10 further Rush the tendency of mouldability.
(adhesive linkage 13)
Adhesive linkage 13 is by layer bonding with metal foil layer 14 for substrate layer 11.Adhesive linkage 13 is via easy to stick Connect process layer 12 bonding with substrate layer 11.Adhesive linkage 13 has for by substrate layer 11 and metal foil layer 14 the most bonding necessary closing forces, and also have when carrying out cold forming for suppression due to Substrate layer 11 and make tracing ability that metal foil layer 14 ruptures (even if also will not for the deformation of member is flexible Peel off ground on component, positively form the performance of adhesive linkage 13).
As constituting the bonding agent of adhesive linkage 13, such as, can use to have and comprise PEPA, poly- The host of the polyhydric alcohol such as ethoxylated polyhydric alcohol, acrylic acid series multiple alcohol and comprise fragrance family, fat family etc. The urethane adhesive of the bi-component curing type of the firming agent of isocyanates.In above-mentioned bonding agent, solidification The mol ratio (=NCO/OH) of the NCO of agent and the hydroxyl of host preferably 1～10, more preferably It is 2～5.
Above-mentioned urethane adhesive after coating, by such as carrying out more than 4 days ripe at 40 DEG C Changing, the hydroxyl of host is carried out with the reaction of the NCO of firming agent, substrate layer 11 and metal foil layer The more strong bond of 14 is possibly realized.
From the viewpoint of obtaining desired adhesive strength, tracing ability and processability etc., adhesive linkage 13 Thickness be preferably 1～10 μm, more preferably 2～6 μm.
(metal foil layer 14)
As metal foil layer 14, the various metal formings of aluminum and rustless steel etc. can be listed, from moisture resistance and From the standpoint of the processabilities such as ductility and cost, metal foil layer 14 is preferably aluminium foil.Aluminium foil is permissible It is general soft aluminium foil, but from the standpoint of the ductility when pinhole resistance and molding is excellent, preferably For comprising the aluminium foil of ferrum.
Comprising in the aluminium foil (100 mass %) of ferrum, the content of ferrum is preferably 0.1～9.0 mass %, more It is preferably 0.5～2.0 mass %.It is more than 0.1 mass % by the content of ferrum, it is possible to obtain having more Excellent pinhole resistance and the exterior member 10 of ductility.It is below 9.0 mass % by the content of ferrum, The more excellent exterior member of flexibility 10 can be obtained.
It addition, as aluminium foil, from the standpoint of the ductility in time can giving desired molding, more Be preferable to carry out annealing soft aluminium foil (such as by 8021 materials described in JIS standard, 8079 The aluminium foil that material is made).
In order to obtain desired electrolyte resistance, the metal forming used in metal foil layer 14 is preferred Implement such as ungrease treatment.It addition, in order to make manufacturing process easy, as above-mentioned metal forming, preferably The most etched metal forming in surface.As above-mentioned ungrease treatment, such as can use wet type ungrease treatment or Dry type ungrease treatment, but from the viewpoint of making manufacturing process's simplicity, preferred dry ungrease treatment.
As above-mentioned dry type ungrease treatment, include, for example out in the operation that metal forming is made annealing treatment In process the time method that carries out ungrease treatment by prolongation.Even if in order to by metal forming softening During the annealing implemented, under the ungrease treatment degree carried out at the same time, also can obtain sufficient electrolyte resistance Property.
It addition, as above-mentioned dry type ungrease treatment, it is possible to use as the place beyond above-mentioned annealing The flame treatment of reason and sided corona treatment etc. process.And then, as above-mentioned dry type ungrease treatment, the most permissible Use the active oxygen produced when utilizing the ultraviolet that metal forming has been irradiated specific wavelength by polluter Oxidation Decomposition and the ungrease treatment of removing.
As above-mentioned wet type ungrease treatment, such as, acid ungrease treatment, alkali degreasing process etc. can be used to process. As the acid used in above-mentioned acid ungrease treatment, such as, can use sulphuric acid, nitric acid, hydrochloric acid, hydrogen fluorine The mineral acids such as acid.These acid can be used alone a kind, it is possible to be two kinds or more.It addition, conduct The alkali that alkali degreasing uses in processing, such as, can use the sodium hydroxide that etch effect is high.Furthermore it is possible to Use the material of material and the surfactant etc. that have coordinated weak base system to carry out alkali degreasing process.On Stating the wet type ungrease treatment being illustrated can use such as infusion process, spraying process to carry out.
From the standpoint of barrier, pinhole resistance and processability, the thickness of metal foil layer 14 is preferably 9～200 μm, more preferably 15～150 μm, more preferably 15～100 μm.Pass through metal forming The thickness of layer 14 is more than 9 μm, even if be applied with stress by processing and forming, it is also difficult to fracture. It is below 200 μm by the thickness of metal foil layer 14, it is possible to the quality reducing exterior member adds, energy The gravimetric energy density enough suppressing electrical storage device reduces.
(corrosion-proof layer 15a, 15b)
Corrosion-proof layer 15a, 15b play by electrolyte or by electrolyte and the reaction of moisture The corrosion of the metal foil layer 14 caused by Fluohydric acid. produced carries out the effect suppressed.It addition, anticorrosion Process layer 15a and play the effect improving metal foil layer 14 with the closing force of adhesive linkage 13.It addition, anticorrosion Erosion processes layer 15b and plays the effect improving metal foil layer 14 with the closing force sealing adhesive linkage 16.Anticorrosion Erosion process layer 15a and corrosion-proof layer 15b can be the layers of same composition, it is also possible to be differently composed Layer.
Corrosion-proof layer 15a, 15b such as can be by becoming corrosion-proof layer 15a, 15b The layer of mother metal implements ungrease treatment, hot water conversion processing, anodized, chemical conversion treatment, applying implenent There is the application type anti-corrosion treatment of the smears of anti-corrosion capability or these are processed the anticorrosion of combination Process and formed.
Ungrease treatment among above-mentioned process, hot water conversion processing, anodized, particularly hot water Conversion processing and anodized are to make metal forming (aluminium foil) surface dissolve with inorganic agent, form corrosion resistant The process of the metallic compound (aluminium compound (boehmite, alumite)) that erosion property is excellent.Therefore, Such process defines co-continuous from metal foil layer 14 to corrosion-proof layer 15a, 15b owing to obtaining The structure of structure, the most also has the situation in the definition being contained in chemical conversion treatment.
As ungrease treatment, acid defat, alkali degreasing can be listed.As acid defat, use can be listed They individually or are obtained by mixing by the mineral acids such as above-mentioned sulphuric acid, nitric acid, hydrochloric acid, Fluohydric acid. The method etc. of acid defat.It addition, as acid defat, make a sodium bifluoride by using with above-mentioned mineral acid The sour degreasing agent that the fluorochemicals such as ammonium dissolve, it is possible to form the degreasing effect not only having metal foil layer 14 And be the fluoride of the metal of passive state, it is effective in terms of hydrofluoric acid resistance.As alkali degreasing, can List the method using sodium hydroxide etc..
As above-mentioned hot water conversion processing, such as, can use by metal foil layer 14 with the addition of three The boehmite carrying out impregnation process in the boiling water of ethanolamine and obtain processes.At above-mentioned anodic oxidation Reason, such as, can use alumite to process.It addition, as above-mentioned chemical conversion treatment, such as can make With chromate process, zirconium process, titanium process, vanadium process, molybdenum process, calcium phosphate process, Strontium hydrate. Process, cerium process, ruthenium process or by process of their two or more combination.These hot water are turned For change process, anodized, chemical conversion treatment, implement above-mentioned ungrease treatment the most in advance.
Further, as above-mentioned chemical conversion treatment, be not limited to damp process, for example, it is also possible to use at these The method that the inorganic agent used in reason mixes with resinous principle, is coated.It addition, as above-mentioned anticorrosion Erosion processes, and makes its effect for while to greatest extent, from the viewpoint of liquid waste processing, is preferably being coated with Type chromate processes.
Anti-corrosion treatment as the application type of the smears in coating with Corrosion Protection uses Smears, can list containing selected from rare earth element oxide sol, anionic polymer, sun from The smears of at least one in sub-property polymer.Particularly preferably use containing rare earth element oxide molten The method of the smears of glue.
The method using the smears containing rare earth element oxide sol is application type anticorrosion purely Erosion processes, by using the method, even general coating process, it is also possible to metal foil layer 14 Give anticorrosion ability.It addition, the layer using rare earth element oxide sol to be formed is to have metal forming The anticorrosion ability (inhibitor effect) of layer 14 and the material that also is adapted in terms of environment.
In rare earth element oxide sol, liquid dispersion medium is dispersed with rare earth element oxidation The microgranule (such as, mean diameter is the particle of below 100nm) of thing.As rare earth element oxide, Cerium oxide, yittrium oxide, Dineodymium trioxide, lanthana etc. can be listed.Wherein particularly preferred cerium oxide.Thus, The adaptation between metal foil layer 14 can be improved further.As rare earth element oxide sol Liquid dispersion medium, such as can use water, alcohol series solvent, hydrocarbon system solvent, ketone series solvent, ester system The various solvents such as solvent, ether series solvent.Wherein particularly preferred water.In corrosion-proof layer 15a, 15b Contained rare earth element oxide can be used alone a kind or two or more is applied in combination.
About rare earth element oxide sol, in order to make the stably dispersing of rare earth element oxide particle Change, as stably dispersing agent, preferably comprise mineral acid, acetic acid, the Fructus Mali pumilaes such as nitric acid, hydrochloric acid, phosphoric acid Organic acid, their salt etc. such as acid, ascorbic acid, lactic acid.Among these stably dispersing agents, especially Phosphoric acid or phosphate are preferably used.Thereby, it is possible to expect following effect: not only rare earth element oxide The decentralized stabilization of particle, and in the purposes of lithium ion battery exterior member, make use of phosphoric acid Sequestering power and adaptation between metal foil layer 14 improves, molten because of the impact of Fluohydric acid. by catching The metal object ion (passive state formation) that goes out though produced by electrolyte resistance imparting, by low temperatures The cohesiveness raising etc. of the rare earth element oxide skin(coating) the most easily causing the dehydrating condensation of phosphoric acid and produce Effect.As can be used as phosphoric acid or the phosphate of stably dispersing agent, include, for example out orthophosphoric acid, Jiao Phosphoric acid, Metaphosphoric acid, their alkali metal salt, ammonium salt etc..The most especially, three Metaphosphoric acids, four inclined phosphorus The condensed phosphoric acids such as acid, hexa metaphosphoric acid, super Metaphosphoric acid or their alkali metal salt and ammonium salt to as lithium from It is preferred that the function of sub-battery exterior member manifests.Especially, if it is considered that use and comprise terres rares The coating composition of element oxide colloidal sol, various rubbing method is used to form the layer comprising rare-earth oxide Time dry film (drying capacity, heat) of making, then the preferred reactive excellent reagent under low temperature, From the standpoint of dehydrating condensation from low temperature is excellent, particular certain cancers.As phosphate, the most water-soluble The salt of property.Phosphoric acid contained in corrosion-proof layer 15a, 15b or phosphate can be used alone 1 Plant or two or more is applied in combination.
In rare earth element oxide sol, as phosphoric acid or the use level of its salt, relative to terres rares Element oxide 100 mass parts, more than preferably 1 mass parts, more than more preferably 5 mass parts.As Fruit is more than 1 mass parts, then the stabilisation of colloidal sol is good, and readily satisfies as lithium ion battery use The function of exterior member.Phosphoric acid or the cooperation of its salt relative to rare earth element oxide 100 mass parts As long as the upper limit is without the scope of the function reduction of rare earth element oxide sol, relative to dilute Great soil group element oxide 100 mass parts, below preferably 100 mass parts, more preferably 50 mass parts Hereinafter, more preferably below 20 mass parts.
But, above-mentioned rare earth element oxide sol the layer formed is due to the set for inorganic particulate Body, therefore even across the operation of dry solidification, the cohesiveness of this layer self is the lowest.Therefore, in order to mend Fill the cohesiveness of this layer, preferably make its Composite with anionic polymer.
As anionic polymer, the polymer with carboxyl can be listed, include, for example out poly-(first Base) acrylic acid (or its salt) or carry out copolymerization using poly-(methyl) acrylic acid as main constituent and form Copolymer.As the copolymer composition of this copolymer, (methyl) alkyl acrylate system can be listed single Body (as alkyl, can list methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, The tert-butyl group, 2-ethylhexyl, cyclohexyl etc..)；(methyl) acrylamide, N-alkyl (methyl) third Acrylamide, N, N-dialkyl group (methyl) acrylamide (as alkyl, can list methyl, ethyl, N-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, 2-ethylhexyl, cyclohexyl etc..)、N- Alkoxyl (methyl) acrylamide, N, N-dialkoxy (methyl) acrylamide, (as alcoxyl Base, can list methoxyl group, ethyoxyl, butoxy, isobutoxy etc..), N-methylol (methyl) The monomer containing acylamino-such as acrylamide, N-phenyl (methyl) acrylamide；(methyl) acrylic acid The monomer containing hydroxyl such as 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester；(methyl) acrylic acid The monomer containing glycidyl such as ethylene oxidic ester, allyl glycidyl ether；(methyl) propylene Acryloxypropylethoxysilane trimethoxy silane, (methyl) acryloxypropyl triethoxysilane etc. are containing silicon The monomer of alkane；The monomer etc. containing NCO such as (methyl) acryloxypropyl isocyanates. It addition, styrene, α-methyl styrene, vinyl methyl ether, EVE, horse can be listed Come sour, maleic acid alkyl monoester, fumaric acid, fumaric acid alkyl monoester, itaconic acid, itaconic acid alkyl list Ester, (methyl) acrylonitrile, vinylidene chloride, ethylene, propylene, vinyl chloride, vinylacetate, fourth two Alkene etc..
Anionic polymer plays at the anticorrosion making employing rare earth element oxide sol and obtain The stability-enhanced effect of reason layer 15a, 15b (oxide skin(coating)).This is by with acrylic acid series tree The effect of the oxide skin(coating) that the protection of fat composition is hard and crisp and seizure are from institute in rare-earth oxide colloidal sol Phosphatic ionic contamination (particularly sodium ion) (cation capture agent) effect contained realizes. That is, if in corrosion-proof layer 15a obtained at use rare earth element oxide sol, 15b Containing alkali metal ion or alkaline-earth metal ions such as particularly sodium, then with the place that comprises this ion for Point, makes corrosion-proof layer 15a, 15b become easily and deteriorates.Therefore, by being polymerized with anionic property Thing by immobilizations such as sodium ion contained in rare-earth oxide colloidal sol, thus corrosion-proof layer 15a, The toleration of 15b improves.
Corrosion-proof layer 15a that combines with anion based polymer and rare earth element oxide sol, 15b has corrosion-proof layer 15a, the 15b formed with metal foil layer 14 is implemented chromate process Equal Corrosion Protection.Anion based polymer preferably will be essentially water miscible polyanion system The structure of crosslinked polymer.As the cross-linking agent used in the formation of this structure, include, for example Go out to have NCO, glycidyl, carboxyl, the compound of oxazoline base.Can also be further Silane coupler is used to import the cross-linking part with siloxane bond.
As having the compound of NCO, include, for example out toluene di-isocyanate(TDI), benzene two sub- Methyl diisocyanate or its hydride, hexamethylene diisocyanate, 4,4 '-diphenyl methane Diisocyanate or its diisocyanates such as hydride, isophorone diisocyanate；Or make these The addition product of isocyanates and the polyol reactions such as trimethylolpropane, obtain by reacting with water The biuret body that arrives or the polyisocyanates such as isocyanuric acid ester body as trimer；Or by this The blocked polyisocyanates etc. of the end-blockingizations such as a little polyisocyanates alcohols, lactams, oximes.
As having the compound of glycidyl, include, for example ethylene glycol of sening as an envoy to, diethylene glycol, three sweet Alcohol, Polyethylene Glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, BDO, 1, The epoxide of the glycolss such as 6-hexanediol, neopentyl glycol and chloropropylene oxide effect, make glycerol, poly- The ring of the polyalcohols such as glycerol, trimethylolpropane, tetramethylolmethane, sorbitol and chloropropylene oxide effect Oxygen compound, the dicarboxylic acids such as phthalic acid, p-phthalic acid, oxalic acid, adipic acid and chloropropylene oxide is made to make With epoxide etc..
As having the compound of carboxyl, various aliphatic or aromatic dicarboxylic acid etc. can be listed, and then It is used as poly-(methyl) acrylic acid and poly-(methyl) acrylic acid alkali (great soil group) slaine.
As having the compound of oxazoline base, include, for example out and there are more than 2 oxazoline unit Low molecular compound or make using in the case of the such polymerizable monomer of isopropenyl oxazoline The acrylic acid such as (methyl) acrylic acid, (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester It it is the compound of monomer copolymerization.
As silane coupler, γ-glycidoxypropyltrime,hoxysilane, γ-epoxy third can be listed Epoxide propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-chlorine third Methoxylsilane, vinyl trichlorosilane, γ mercaptopropyitrimethoxy silane, gamma-amino propyl group three Ethoxysilane, N-β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, γ-NCO third Ethyl triethoxy silicane alkane, when particularly considering with anionic polymer reactive, preferably epoxy silane, Amino silane, isocyanato silanes.
The use level of cross-linking agent is preferably 1～50 mass relative to anionic polymer 100 mass parts Part, more preferably 10～20 mass parts.If the ratio of cross-linking agent is relative to anionic polymer 100 Mass parts is more than 1 mass parts, is the most easily adequately formed cross-linked structure.If the ratio phase of cross-linking agent Be below 50 mass parts for anionic polymer 100 mass parts, then the working life (pot life) of masking liquid Improve.
The method making anionic polymer cross-link is not limited to above-mentioned cross-linking agent, it is also possible to be use titanium, Zirconium compounds forms the method etc. of ionomer.It addition, these materials can apply formation anti-corrosion treatment The coating composition of layer 15a.
In corrosion-proof layer 15a illustrated above with, 15b, by being processed as generation with chromate The chemical conversion treatment of table and obtain corrosion-proof layer 15a, 15b is owing to being formed and the inclining of metal foil layer 14 Biassed fabric, uses the most especially and has coordinated Fluohydric acid., hydrochloric acid, nitric acid, sulphuric acid or the change of their salt Become inorganic agent that metal foil layer 14 enforcement is processed, next make the compound of chromium system or non-chromium play and make With, chemical conversion treatment layer is formed on metal foil layer 14.But, above-mentioned chemical conversion treatment is due in chemical conversion Inorganic agent uses acid, therefore with deterioration and the corrosion of apparatus for coating of working environment.
On the other hand, corrosion-proof layer 15a of aforesaid application type, 15b are processed as with chromate The chemical conversion treatment represented is different, it is not necessary to form incline structure for metal foil layer 14.Therefore, smears Character will not be by acid, alkaline, neutral etc. restriction, it is possible to realize good working environment.This Outward, in environmental health, require replacement case from the standpoint of, use chromium compound chromate process also Preferably corrosion-proof layer 15a of application type, 15b.
Corrosion-proof layer 15a, 15b can be formed as required further by cation property copolymer stacking Stepped construction.As cation property copolymer, polymine can be listed, by polymine and There is the ion high-molecular complex of the polymer composition of carboxylic acid, make primary amine connect in acrylic acid series main framing Grafting of primary amines acrylic resin, polyallylamine or their derivant, the amino phenols resin etc. of branch.
As " there is the polymer of carboxylic acid " of formation ion high-molecular complex, include, for example out poly- Carboxylic acid (salt), in polycarboxylic acids (salt), imported comonomer and obtain copolymer, there is carboxyl Polysaccharide etc..As polycarboxylic acids (salt), include, for example out polyacrylic acid or its ion salt etc..Make For having the polysaccharide of carboxyl, include, for example out carboxymethyl cellulose or its ion salt etc..As ion Salt, can list alkali metal salt, alkali earth metal salt etc..
Grafting of primary amines acrylic resin is to make grafting of primary amines to the resin in acrylic acid series main framing. As this acrylic acid series main framing, poly-(methyl) acrylic acid etc., above-mentioned acrylic acid series can be listed many The various monomers used in unit's alcohol.As the primary amine of grafting in this acrylic acid series main framing, can list Aziridine etc..
As polyallylamine or derivatives thereof, it is possible to use allylamine, allylamine amido sulfuric acid salt, diene The homopolymer of propylamine, dimethyl allylamine etc. or copolymer, and then, for these amine, free amine Can use with the stable compound formed with acetic acid or hydrochloric acid.It addition, become as further copolymer Point, it is possible to use maleic acid, sulfur dioxide etc..And then can also use by making primary amine moiety methoxy Base and impart the type of heat cross-linking.These cation property copolymers can be used alone a kind, Can also be two kinds or more.As cation property copolymer, in above-mentioned, it is preferably selected from polyene third At least one in base amine and derivant thereof.
Cation property copolymer preferably with there is carboxyl, glycidyl etc. can be with amine/imine reaction The cross-linking agent of functional group is also used.As the cross-linking agent with cation property copolymer, it is possible to use tool There is the polymer of the carboxylic acid forming ion high-molecular complex with polymine, include, for example out poly-third The polycarboxylic acids (salt) such as olefin(e) acid or its ion salt or imported in these comonomer copolymer, Carboxy methyl cellulose or its ion salt etc. have the polysaccharide etc. of carboxyl.
In present embodiment, cation property copolymer be also recited as constitute corrosion-proof layer 15a, One element of 15b.It reason for this is that, in order to give required by lithium ion battery exterior member Electrolyte resistance, hydrofluoric acid resistance, use various compound to conduct in-depth research, result distinguish sun from Sub-property polymer self is also the compound that can give electrolyte resistance, hydrofluoric acid resistance.Speculate that it is main Want reason to be, by catching fluorion (anion catching agent) with cationic base, thus inhibit Metal foil layer 14 damages.It addition, cation property copolymer is improving corrosion-proof layer 15b and sealing The aspect of the cementability of adhesive linkage 16 is also highly preferred.It addition, cation property copolymer due to Aforesaid anionic polymer is similarly water solublity, therefore by using above-mentioned cross-linking agent to form crosslinking Structure such that it is able to improve resistance to water.Hand over such that use cation property copolymer also is able to be formed Connection structure, is therefore being used for the formation of corrosion-proof layer 15a, 15b by rare-earth oxide colloidal sol In the case of, as its protective layer, anionic polymer can be replaced to use cation property copolymer.
From above content, as the example of combination of the anti-corrosion treatment of above-mentioned application type, can List (1) and only have rare-earth oxide colloidal sol, (2) only anionic polymer, (3) only Cation property copolymer, (4) rare-earth oxide colloidal sol+anionic polymer (stacking Composite), (5) rare-earth oxide colloidal sol+cation property copolymer (stacking Composite), (6) (terres rares oxidation Thing colloidal sol+anionic polymer: stacking Composite)/cation property copolymer (multiple stratification), (7) are (dilute Great soil group oxide sol+cation property copolymer: stacking Composite)/anionic polymer (multiple stratification) Deng.Wherein it is particularly preferred to (1) and (4)～(7), more preferably (4)～(7).It addition, In the case of corrosion-proof layer 15a, owing to anticorrosion ability and anchoring effect can be realized further (adaptation raising effect), therefore particularly preferably (6).It addition, in the feelings of corrosion-proof layer 15b Under condition, owing to becoming easier to keep the electrolyte resistance of sealant 17 side, therefore particularly preferably (6) And (7).But, present embodiment is not limited to combinations thereof.Such as, as the choosing of anti-corrosion treatment The example selected, cation property copolymer is owing to being to enumerate in the explanation of sealing adhesive linkage 16 described later The good highly preferred material of aspect of the cementability of modified polyolefin resin, therefore with modified polyolefin In the case of hydrocarbon resin constitutes sealing adhesive linkage 16, can be to set in the face connected with sealing adhesive linkage 16 Put cation property copolymer (such as constituting the composition of (5) and (6) etc.) such design.
But, corrosion-proof layer 15a, 15b are not limited to above-mentioned layer.For example, it is possible to such as conduct The application type chromate of known technology is such, uses and coordinates in resinoid bond (amino phenols resin etc.) The inorganic agent of phosphoric acid and chromium compound is formed.If using this inorganic agent, can be formed and having concurrently Corrosion proof function and the layer of adaptation.It addition, for above-mentioned chemical conversion treatment layer (at defat Reason, hot water conversion processing, anodized, chemical conversion treatment or the shape by the combination of these process The layer become), in order to improve adaptation, it is possible to use above-mentioned cation property copolymer and/or anion Property polymer implement the process that is combined, or for the combination that these process, cationic is polymerized Thing and/or anionic polymer stacking are as multiple structure.Further it is necessary to consider the stability of masking liquid, But can use and above-mentioned rare-earth oxide colloidal sol is polymerized with cation property copolymer or anionic property Formal matter elder generation one pack system and the smears that obtains forms the layer having corrosion proof function and adaptation concurrently.
Corrosion-proof layer 15a, the Functionality, quality and appealing design of per unit area of 15b elect 0.005～0.200g/m as2 In the range of, more preferably 0.010～0.100g/m2In the range of.If 0.005g/m2Above, Easily give corrosion proof function to metal foil layer 14.Even if it addition, the quality of above-mentioned per unit area surpasses Cross 0.200g/m2, corrosion proof function is saturated, also will not change very much.On the other hand, terres rares is employed In the case of oxide sol, if being coated with thickness, then become insufficient by thermally-induced solidification time dry, Likely with the reduction of cohesiveness.It should be noted that by the quality of per unit area in foregoing Recorded, but if it is known that if proportion, it is also possible to by its conversion thickness.
From corrosion proof function and as the function of Anchor Agent from the standpoint of, corrosion-proof layer 15a, 15b Thickness such as be preferably 10nm～5 μm, more preferably 20～500nm.
(sealing adhesive linkage 16)
Sealing adhesive linkage 16 is to define metal foil layer 14 and the sealant of corrosion-proof layer 15b 17 bonding layers.According to formed seal adhesive linkage 16 bonding composition difference and by exterior member 10 It is roughly divided into hot laminating to constitute and dry lamination composition.
The bonding composition sealing adhesive linkage 16 formed during hot laminating is constituted is preferably polyolefin-based resins The acid modified polyolefin system resin of graft modification has been carried out with acid.Acid modified polyolefin system resin is due to by pole Property group imported in the part of non-polar polyolefin-based resins, therefore, it is possible to by non-polar poly- Olefin-based resin molding etc. constitute time sealant 17 and have more polarity corrosion-proof layer 15b this two Person is the most closely sealed.It addition, by using acid modified polyolefin system resin, exterior member 10 is to electrolysis The toleration of the contents such as liquid improves, even if producing Fluohydric acid. at inside battery, the most easily prevents by sealing The reduction of the closing force that the deterioration of adhesive linkage 16 is caused.
As the polyolefin-based resins of acid modified polyolefin system resin, include, for example out low-density, in close Degree and highdensity polyethylene；Ethylene-alpha-olefin copolymer；Polypropylene；And propylene-alpha olefin copolymerization Thing etc..Can be block copolymer for vistanex during copolymer, it is also possible to be random copolymer. It addition, as vistanex, it is possible to use make acrylic or methacrylic acid isopolarity molecule with upper The polymer etc. of the copolymer of the vistanex copolymerization stated or cross-linked polyolefin etc..As right The acid that polyolefin-based resins is modified, can list carboxylic acid, epoxide and anhydride etc., is preferably Maleic anhydride.The acid modified polyolefin system resin used in sealing adhesive linkage 16 can be a kind, also Can be two or more.
The sealing adhesive linkage 16 that hot laminating is constituted can be by extruding above-mentioned bonding composition with extrusion device And formed.The thickness sealing adhesive linkage 16 that hot laminating is constituted is preferably 2～50 μm.
As formed dry lamination constitute seal adhesive linkage 16 bonding composition, include, for example out with The bonding agent that the bonding composition enumerated in adhesive linkage 13 is same.In this case, in order to suppress by electricity Solve the hydrolysis that is swelling and that caused that causes of liquid by Fluohydric acid., preferably with the host of the skeleton of not facile hydrolysis and Become the composition that can design bonding agent in the way of improving the composition of crosslink density.
In the case of making crosslink density improve, such as, can add dimer (fatty acid) yl, dimerization in bonding agent The ester of fatty acid or hydride, reduction glycol, the ester of dimer (fatty acid) yl or the hydride of dimer (fatty acid) yl Reduction glycol.Above-mentioned dimer (fatty acid) yl is the acid making various unsaturated fatty acid dimerization, as its structure, Non-ring-like, mononuclear type, how ring-like, fragrant ring-like can be illustrated.
The fatty acid of the parent material as dimer (fatty acid) yl is not particularly limited.Alternatively, it is also possible to The binary acid used in common PEPA, as neccessary composition, is led by such dimer (fatty acid) yl Enter.As the firming agent for constituting the host sealing adhesive linkage 16, it is, for example possible to use also be able to The isocyanate compound used as the chain extender of PEPA.Thus, the crosslinking of bonding agent film Density improves, and causes the raising of dissolubility and swellability, is improved by carbamate groups concentration simultaneously, It also is able to expect the raising of base material adaptation.
The sealing adhesive linkage 16 that dry lamination is constituted is water-disintegrable owing to having ester group and carbamate groups etc. High joint portion, therefore in the purposes requiring higher reliability, is preferably used the viscous of hot laminating composition It is connected into and is allocated as sealing adhesive linkage 16.Such as by by acid-modified polyolefin resin toluene, methyl Hexamethylene (MCH) equal solvent dissolves or coordinates above-mentioned various firming agent in the masking liquid of dispersion, It is coated with, is dried, thus form sealing adhesive linkage 16.
Formed in the case of sealing adhesive linkage 16 by extrusion molding, should due to produce during extrusion molding Power etc., adhering resin is easily in MD direction (extrusion direction) upper orientation.In this case, in order to slow With the anisotropy of sealing adhesive linkage 16, elastomer can be coordinated in sealing adhesive linkage 16.As close The elastomer coordinated in envelope adhesive linkage 16, such as, can use olefin-based elastomer, polystyrene elastic Body etc..
The mean diameter of above-mentioned elastomer preferably can improve elastomer and adhering resin the compatibility and And the particle diameter relaxing the anisotropic effect sealing adhesive linkage 16 can be improved.Specifically, above-mentioned The mean diameter of elastomer is such as preferably below 200nm.
It should be noted that the mean diameter of elastomer is such as obtained by following method: use electronics The photo that the cross section of elastic composition is amplified by microscope photographing, then, by image analysis, to dividing The mean diameter of the crosslinking rubber constituent dissipated is measured.Above-mentioned elastomer can be used alone a kind, Also two or more may be used uses.
In the case of coordinating elastomer in sealing adhesive linkage 16, sealing adhesive linkage 16 (100 mass The use level of the elastomer added in %) is such as preferably 1～25 mass %, more preferably 10～20 Quality %.It is more than 1 mass % by making the use level of elastomer, there is following tendency: with viscous The anisotropic effect raising sealing adhesive linkage 16 is relaxed while connecing the compatibility raising of resin.Separately Outward, it is below 25 mass % by making the use level of elastomer, there is suppression sealing adhesive linkage 16 electric Solve the tendency that the swelling effect of liquid improves.
As sealing adhesive linkage 16, such as, adhering resin can be used to disperse in organic solvent to form Dispersion type adhering resin liquid.
In the case of hot laminating is constituted, the thickness sealing adhesive linkage 16 is preferably more than 8 μm 50 μm Hereinafter, below more than more preferably 20 μm 40 μm.It is 8 μm by sealing the thickness of adhesive linkage 16 Above, the sufficient adhesive strength of metal foil layer 14 and sealant 17 it is readily available；Bonding by sealing The thickness of layer 16 is below 50 μm, it is possible to easily reduce from the battery within the immersion of exterior member end face Water quantities in unit.It addition, in the case of dry lamination is constituted, seal the thickness of adhesive linkage 16 It is preferably below more than 1 μm 5 μm.It is more than 1 μm by sealing the thickness of adhesive linkage 16, easily Obtain the sufficient adhesive strength of metal foil layer 14 and sealant 17；By sealing the thickness of adhesive linkage 16 Degree is below 5 μm, it is possible to suppression seals the generation of the crackle of adhesive linkage 16.
(sealant 17)
Sealant 17 is layer exterior member 10 being given to the sealing produced by heat-sealing, and it is to store It is configured in inner side during the assembling of electric installation and makes the layer of its heat fused.As sealant 17, can enumerate Go out by polyolefin-based resins or make the acid graft modification such as maleic anhydride in polyolefin-based resins The resin molding that acid modified polyolefin system resin is made.Wherein it is particularly preferred to make the barrier of water vapour carry High, can be at the polyolefin of the form that will not constitute electrical storage device because of heat-sealing in the case of being exceedingly squashed It is resin, particularly preferred polypropylene.
As polyolefin-based resins, include, for example out low-density, Midst density and highdensity polyethylene； Ethylene-alpha-olefin copolymer；Polypropylene；And propylene-alpha olefin copolymer etc..For gathering during copolymer Olefin resin can be block copolymer, it is also possible to be random copolymer.These polyolefin-based resins are permissible It is used alone a kind, it is possible to be two kinds or more.
It addition, at the above-mentioned i.e. random polypropylene of all types of polypropylene, HOPP, block polypropylene In can add the ethylene-butene copolymer of low-crystalline, the propene-1-butene copolymer of low-crystalline, by second The ter-polymers of 3 composition copolymers compositions of alkene, butylene and propylene, silicon dioxide, zeolite, propylene Acid is the anti-blocking agents such as resin beads (AB agent), the lubricant etc. of fatty acid amide system.
As acid modified polyolefin system resin, include, for example out and seal the tree enumerated in adhesive linkage 16 The resin that fat is same.
Sealant 17 can be monofilm, it is also possible to be multilayer film, can be according to required function selecting. Such as, at the aspect giving moisture resistance, it is possible to use and wherein there is ethylene-cyclic olefin copolymer and gather The multilayer film of the resins such as methylpentene.
It addition, sealant 17 can to contain fire retardant, lubricant, anti-blocking agent, antioxidant, light steady Determine the various interpolation materials such as agent and bonding imparting agent.
As sealant 17, in the case of using the heat fused film formed by extrusion molding, at this There is orientation tendency in the extrusion direction of heat fused film.Therefore, the sealant caused by orientation from mitigation From the viewpoint of the anisotropy of 17, elastomer can be coordinated in heat fused film.Thereby, it is possible to press down When system carries out cold forming to electrical storage device exterior member 10 and forms recess there is albefaction in sealant 17.
As the elastomer of composition sealant 17, such as, can use and seal adhesive linkage 16 with as constituting The identical material of the material illustrated in elastomer.In the case of sealant 17 is multi-layer film structure, Constituting in multiple layers of multi-layer film structure, at least 1 layer can be constituted in the way of comprising elastomer.Such as, As sealant 17, it is being made up of the random polypropylene layer of stacking/block polypropylene layer/random polypropylene layer 3 multilayer laminated structure in the case of, elastomer can only be matched with in block polypropylene layer, it is possible to only coordinates In random polypropylene layer, it is also possible to coordinate in both random polypropylene layer and block polypropylene layer.
It addition, in order to give lubricity to sealant 17, lubricant can be contained.So, by sealing Layer 17 is containing lubricant, by cold forming when electrical storage device is with formation recess in exterior member 10, and can The limit that become recess high with extensibility in suppression electrical storage device exterior member 10 or the part at angle are by mistake The stretching of degree ground.Thereby, it is possible to suppress metal foil layer 14 and seal stripping, sealant between adhesive linkage 16 17 and seal in adhesive linkage 16 fracture and the albefaction occurring to be caused by crackle.
In the case of containing lubricant in making sealant 17, in sealant 17 (100 mass %) The content of lubricant preferably 0.001 mass %～0.5 mass %.If the content of lubricant is 0.001 matter , then there is the tendency of sealant 17 albefaction when can suppress cold forming further in amount more than %.Additionally, If the content of lubricant is below 0.5 mass %, then exist can suppress with and the face of sealant 17 connect The tendency of the reduction of the dhering strength between the face of other the layer touched.
The thickness of sealant 17 is preferably 10～100 μm, more preferably 20～60 μm.Pass through sealant The thickness of 17 is more than 20 μm, it is possible to obtain sufficient heat seal strength；Thickness by sealant 17 It is below 90 μm, it is possible to reduce the amount of the water vapour immersed from exterior member end.
[manufacture method of exterior member]
It follows that the manufacture method of exterior member 10 is illustrated.It should be noted that exterior structure The manufacture method of part 10 is not limited to following method.
As the manufacture method of exterior member 10, include, for example out and there is following operation S11～S14 Method.
Operation S11: form corrosion-proof layer 15a in the one side of metal foil layer 14, at metal foil layer The operation of corrosion-proof layer 15b is formed on the another side of 14.
Operation S12: form easy bonding process layer 12 in the one side of substrate layer 11, obtain duplexer Operation.
Operation S13: via contrary with metal foil layer 14 by corrosion-proof layer 15a of adhesive linkage 13 The operation of the face laminating of the face of side and easy to be bonding process layer 12 side of above-mentioned duplexer.
Operation S14: via seal adhesive linkage 16 in corrosion-proof layer 15b with metal foil layer 14 The operation of sealant 17 is formed on the face of opposition side.
(operation S11)
In operation S11, the one side of metal foil layer 14 forms corrosion-proof layer 15a, at metal Corrosion-proof layer 15b is formed on the another side of layers of foil 14.Corrosion-proof layer 15a and 15b are permissible Each it is respectively formed, it is also possible to both once are formed.Specifically, such as, by metal It is coated with anti-corrosion treatment agent (mother metal of corrosion-proof layer) on the two sides of layers of foil 14, then, enters successively Row is dried, solidifies, sinters, thus once forms corrosion-proof layer 15a and 15b.It addition, can To be coated with anti-corrosion treatment agent in the one side of metal foil layer 14, it is dried successively, solidifies, sinters, After defining corrosion-proof layer 15a, the another side of metal foil layer 14 is identically formed anticorrosion Process layer 15b.There is no particular restriction for the formation order of corrosion-proof layer 15a and 15b.It addition, close In anti-corrosion treatment agent, can use different in corrosion-proof layer 15a and corrosion-proof layer 15b Anti-corrosion treatment agent, it is possible to use identical anti-corrosion treatment agent.As above-mentioned anti-corrosion treatment agent, example Such as the anti-corrosion treatment agent etc. that application type chromate can be used to process.Coating to anti-corrosion treatment agent Method is not particularly limited, such as can use gravure coating process, reverse gravure coating process, rolling method, Reverse rollers coating, mouth die coating method, bar type rubbing method, lick coating, the unfilled corner wheel method such as rubbing method. Further, as metal foil layer 14, untreated metal foil layer can be used, it is possible to use taken off by wet type Fat process or dry type ungrease treatment implement the metal foil layer of ungrease treatment.
(operation S12)
In operation S12, the one side of substrate layer 11 forms easy bonding process layer 12.Here, conduct One example of the forming method of easy bonding process layer 12, illustrates for streamline rubbing method.First First, prepare the above-mentioned resin dispersant containing the main constituent by becoming easy bonding process layer 12 and The aqueous coating fluid of the dispersion become.It follows that the thermoplastic resin film (base before crystalline orientation completes The mother metal of sheet material layers 11) one side on be coated with above-mentioned aqueous coating fluid.It follows that make the above-mentioned water of coating Property coating fluid is dried, and is then stretched at least one direction of principal axis by thermoplastic resin film.
It follows that by heat treatment, make the orientation of thermoplastic resin film complete, thus obtain at substrate layer The duplexer of easy bonding process layer 12 is defined in the one side of 11.By using such streamline to be coated with Method forms easy bonding process layer 12, and the adaptation between substrate layer 11 with easy bonding process layer 12 improves. Further, the forming method of easy bonding process layer 12 is not limited to said method, any method can be used. It addition, the opportunity forming easy bonding process layer 12 is not limited to present embodiment.
(operation S13)
In operation S13, by corrosion-proof layer 15a with the face of the opposition side of metal foil layer 14 and upper It is dry that the face of easy to be bonding process layer 12 side stating duplexer uses the bonding agent for forming adhesive linkage 13 to use The method laminatings such as formula lamination.In operation S13, in order to promote cementability, can be at room temperature～the model of 100 DEG C Carry out ripening (health preserving) in enclosing to process.For example, 1～10 day curing time.
(operation S14)
After operation S13, at by substrate layer 11, easy bonding process layer 12, adhesive linkage 13, anticorrosion The anticorrosion of the duplexer that reason layer 15a, metal foil layer 14 and corrosion-proof layer 15b stack gradually Erosion processes on the face with the opposition side of metal foil layer 14 of layer 15b, is formed close via sealing adhesive linkage 16 Sealing 17.Sealant 17 can carry out stacking by dry lamination and interlayer lamination etc., it is possible to bonding with sealing Layer 16 carrys out stacking by coetrusion together.From the standpoint of cementability improves, sealant 17 is preferred Such as carry out stacking by interlayer lamination or carry out stacking by coetrusion together with sealing adhesive linkage 16, More preferably carry out stacking by interlayer lamination.
By operation S11 illustrated above with～S14, obtain exterior member 10.Should illustrate , the process sequence of the manufacture method of exterior member 10 be not limited to implement successively above-mentioned operation S11～ The method of S14.Such as, operation S11 etc. can be carried out after carrying out operation S12 and suitably change enforcement The order of operation.
[electrical storage device]
It follows that illustrate possessing the exterior member 10 electrical storage device as container.Electrical storage device Possess: the battery unit 1 comprising electrode, the lead-in wire 2 extended out from above-mentioned electrode and receiving battery list Unit 1 container, wherein, said vesse by electrical storage device exterior member 10 so that sealant 17 becomes Mode for inner side is formed.Said vesse can be by making sealant 17 relative to each other 2 exterior member Overlap to ground, make the circumference heat fused of the exterior member 10 of overlap obtain, also by by 1 Exterior member turns down and overlaps, and is similarly obtained by the circumference heat fused of exterior member 10.It addition, Electrical storage device can possess exterior member 20 as container.As electrical storage device, include, for example out lithium from The electrochemical capacitors such as secondary cell and double layer capacitor such as sub-battery, Ni-MH battery and lead battery Device.
Lead-in wire 2 is clamped by the exterior member 10 forming container with sealant 17 for inner side, seals.Draw Line 2 can be clamped by exterior member 10 via lug fluid sealant.
[manufacture method of electrical storage device]
It follows that the method using above-mentioned exterior member 10 to manufacture electrical storage device is illustrated.Need It is noted that here, manufacture as a example by the situation of secondary cell 40 by use pattern pressing type exterior member 30 Illustrate.Fig. 2 is the figure representing above-mentioned pattern pressing type exterior member 30.(a)～(d) of Fig. 3 It it is the axonometric chart of the manufacturing process representing the unilateral processing and forming battery employing exterior member 10.As Secondary cell 40, can be by arranging 2 such exterior member of pattern pressing type exterior member 30, The both sides processing and forming battery while adjusting alignment, such exterior member fitted each other and manufacture.Separately Outward, pattern pressing type exterior member 30 can use exterior member 20 to be formed.
As unilateral processing and forming battery secondary cell 40 such as can by following operation S21～ S25 manufactures.
Operation S21: prepare exterior member 10, the battery unit 1 comprising electrode and prolong from above-mentioned electrode The operation of the lead-in wire 2 stretched.
Operation S22: form the recess 32 for configuring battery unit 1 on the one side of exterior member 10 Operation (with reference to Fig. 3 (a) and Fig. 3 (b)).
Operation S23: configure battery in the processing and forming region (recess 32) of pattern pressing type exterior member 30 By pattern pressing type exterior member 30 turnover, unit 1, overlaps such that recess 32 is covered by cap 34, with Clamp the mode of the lead-in wire 2 extended out from battery unit 1 by pattern pressing type exterior member 30 while adding The operation (with reference to Fig. 3 (b) and Fig. 3 (c)) of pressure heat fused.
Operation S24: make the residual beyond by the limit of lead-in wire 2 clamping, by other limit pressurized heat fusions, Then from that remain while injecting electrolyte, under vacuum conditions by the work of the pressurized heat fusion of residual Sequence (with reference to Fig. 3 (c)).
Operation S25: the pressurized heat beyond the limit of clamp leads 2 is fused end, limit and cuts away, add to molding The operation (with reference to Fig. 3 (d)) of territory, work area (recess 32) side warpage.
(operation S21)
In operation S21, prepare exterior member 10, comprise the battery unit 1 of electrode and from above-mentioned electricity The lead-in wire 2 that pole extends out.Exterior member 10 is to prepare based on above-mentioned embodiment.As Battery unit 1 and lead-in wire 2, there is no particular restriction, it is possible to use known battery unit 1 and lead-in wire 2.
(operation S22)
In operation S22, formed for configuring battery unit 1 in sealant 17 side of exterior member 10 Recess 32.The flat shape making recess 32 is the shape that the shape with battery unit 1 is consistent, such as, bow Depending on rectangular-shaped.Recess 32 is such as by having the extruded member of rectangular-shaped pressure face relative to exterior A part for component 10 carries out extruding being formed in the thickness direction thereof.It addition, the position carrying out extruding, I.e. recess 32 is from the longitudinal direction of the mediad exterior member 10 cut out as rectangular exterior member 10 Formed on the position of one end biasing.Thereby, it is possible to recess 32 will be formed without after processing and forming The other end rollover folding, forms lid (cap 34).
As the method forming recess 32, more specifically, can list and employ the molding of mould and add Work (deep-draw molding).As forming method, can list use with the thickness with exterior member 10 with On the former that configures of the mode in gap and the mould of formpiston, by the mould of formpiston and exterior member 10 1 Play the method in the mould of press-in former.By adjusting the intrusion of the mould of formpiston, can be by recess The degree of depth (deep-draw amount) of 32 is adjusted to desired amount.By forming recess 32 in exterior member 10, Thus obtain pattern pressing type exterior member 30.This pattern pressing type exterior member 30 has such as shown in Fig. 2 Shape.Here, the axonometric chart that Fig. 2 (a) is pattern pressing type exterior member 30, Fig. 2 (b) is along Fig. 2 The longitudinal section of the b-b line of the pattern pressing type exterior member 30 shown in (a).
(operation S23)
In operation S23, configure in the processing and forming region (recess 32) of pattern pressing type exterior member 30 The battery unit 1 being made up of positive pole, barrier film and negative pole etc..It addition, will extend out from battery unit 1 And the lead-in wire 2 engaged with positive pole and negative pole respectively outwards draws from processing and forming region (recess 32). Then, for pattern pressing type exterior member 30, in longitudinal approximate centre turnover, with sealant 17 that This mode becoming inner side is overlapping, by the pressurized heat of the lead-in wire 2 of clamping pattern pressing type exterior member 30 Fusion.Pressurized heat fusion is controlled by 3 conditions of temperature, pressure and time, suitably sets Fixed.The temperature of pressurized heat fusion is preferably more than the temperature melted by sealant 17.
Further, thickness before the heat fused of sealant 17 relative to the thickness of lead-in wire 2 be preferably 40% with Upper and less than 80%.It is more than above-mentioned lower limit by the thickness of sealant 17, there is heat fused resin The tendency of lead-in wire 2 ends can be fully filled；By the thickness of sealant 17 be above-mentioned higher limit with Under, it is possible to moderately control the thickness of exterior member 10 end of secondary cell 40, it is possible to reduce from outward The amount of the moisture that dress component 10 end is immersed.
(operation S24)
In operation S24, make the residual beyond the limit of clamp leads 2, carry out the pressurized heat on other limits Fusion.Then, from the injection electrolyte of residual, one side pressurized heat under vacuum conditions that will remain Fusion.The condition of pressurized heat fusion is as operation S23.
(operation S25)
Periphery pressurized heat fusion end, limit beyond the limit of clamp leads 2 is cut off, and that exposes from end is close Sealing 17 is removed.Then, by folding that periphery pressurized heat fused portion is turned on one's side to processing and forming region 32, Form folding portion 42, thus obtain secondary cell 40.
Excellent to the manufacture method of electrical storage device exterior member of the present utility model and electrical storage device above The embodiment of choosing has been described in detail, but this utility model is not limited to these particular implementation, permissible Various deformation and change is carried out in the range of the purport of the present utility model recorded in detail in the claims.
[embodiment]
Further illustrate this utility model below based on embodiment, but this utility model be not limited to Under embodiment.
(preparation of substrate layer)
As substrate layer 11, the following nylon membrane A-1-1 for preparing to use tubular type biaxial stretching process to manufacture～ A-1-2, B-1-1～B-1-7, C-1-1～C-1-3 and D-1-1～D-1-2.Each nylon membrane described below Thickness, 95 DEG C of hot water shrinkages and 180 DEG C of percent thermal shrinkages.
A-1-1: thickness be 15 μm, 95 DEG C of hot water shrinkages be 3.6%, 180 DEG C of percent thermal shrinkages be 5.3%.
A-1-2: thickness be 15 μm, 95 DEG C of hot water shrinkages be 2.8%, 180 DEG C of percent thermal shrinkages be 3.0%.
B-1-1: thickness be 25 μm, 95 DEG C of hot water shrinkages be 4.0%, 180 DEG C of percent thermal shrinkages be 4.8%.
B-1-2: thickness be 25 μm, 95 DEG C of hot water shrinkages be 4.0%, 180 DEG C of percent thermal shrinkages be 4.8%.
B-1-3: thickness be 25 μm, 95 DEG C of hot water shrinkages be 3.6%, 180 DEG C of percent thermal shrinkages be 9.4%.
B-1-4: thickness be 25 μm, 95 DEG C of hot water shrinkages be 3.7%, 180 DEG C of percent thermal shrinkages be 15.2%.
B-1-5: thickness be 25 μm, 95 DEG C of hot water shrinkages be 2.6%, 180 DEG C of percent thermal shrinkages be 2.7%.
B-1-6: thickness be 25 μm, 95 DEG C of hot water shrinkages be 7.7%, 180 DEG C of percent thermal shrinkages be 15.1%.
B-1-7: thickness be 25 μm, 95 DEG C of hot water shrinkages be 4.8%, 180 DEG C of percent thermal shrinkages be 20.4%.
C-1-1: thickness be 25 μm, 95 DEG C of hot water shrinkages be 4.0%, 180 DEG C of percent thermal shrinkages be 4.8%.
C-1-2: thickness be 25 μm, 95 DEG C of hot water shrinkages be 3.6%, 180 DEG C of percent thermal shrinkages be 9.4%.
C-1-3: thickness be 25 μm, 95 DEG C of hot water shrinkages be 3.7%, 180 DEG C of percent thermal shrinkages be 15.2%.
D-1-1: thickness be 25 μm, 95 DEG C of hot water shrinkages be 3.7%, 180 DEG C of percent thermal shrinkages be 4.5%.
D-1-2: thickness be 25 μm, 95 DEG C of hot water shrinkages be 2.4%, 180 DEG C of percent thermal shrinkages be 2.8%.
(preparation of easy bonding process layer formation smears)
As easy bonding process layer formation smears, prepare the smears of following composition.
Smears: at the water-soluble polyester " ARON MELT PES-1000 " of Toagosei Co., Ltd The middle self-emulsifying type polyisocyanates by Nippon Polyurethane Industry Co., Ltd. " AQUANATE 100 " Spherical shape silicon dioxide microparticle " SEAHOSTAR with Nippon Shokubai Kagaku Kogyo Co., Ltd KE-P30 " (mean diameter is 0.3 μm) match ratio (mass ratio) addition with 95/5/0.5, use water Dilution.
(embodiment 1-1)
In embodiment 1-1, make electrical storage device exterior member 10 by following method.First, As metal foil layer 14, prepare soft aluminium foil 8079 material (Japan's aluminum strain formula meeting that thickness is 40 μm Society manufactures).It follows that use distilled water by gravure coating process coating on the two sides of metal foil layer 14 As solvent and be adjusted to the polyphosphate sodium stabilisation cerium oxide sol that solid point concentration is 10 mass % (anti-corrosion treatment agent).Now, relative to cerium oxide 100 mass parts, making phosphoric acid is 10 mass parts.
It follows that make the polyphosphate sodium stabilisation cerium oxide sol of coating after drying, by burning successively Knot processes, and forms corrosion-proof layer 15a, at metal foil layer 14 in the one side of metal foil layer 14 Corrosion-proof layer 15b is formed on another side.Now, as sintering condition, making temperature is 150 DEG C, Making the process time is 30 seconds.
It follows that as substrate layer 11, use nylon membrane A-1-1, the one side of substrate layer 11 carried out Sided corona treatment.
It follows that the opposition side with metal foil layer 14 of corrosion-proof layer 15a at metal foil layer 14 Face on, coating urethane adhesive as adhesive linkage 13.It follows that by dry lamination method, Via adhesive linkage 13, metal foil layer 14 is bonding with the face that the sided corona treatment of substrate layer 11 is crossed.Then, By will be by substrate layer 11, adhesive linkage 13, corrosion-proof layer 15a, metal foil layer 14 and anticorrosion Process in the atmosphere that construction temperature is 60 DEG C that layer 15b is constituted and place 6 days, thus carried out ripe Change processes.
It follows that on the face with the opposition side of metal foil layer 14 of corrosion-proof layer 15b, coating Acid modified polyolefin in being dissolved in the mixed solvent of toluene and hexahydrotoluene many isocyanides have been coordinated The urethane adhesive of acid esters is as sealing adhesive linkage 16.It follows that by dry lamination method, The polyolefin film that thickness is 40 μm of sealant 17 will be become (to non-stretched via sealing adhesive linkage 16 The face sealing adhesive linkage 16 side of polypropylene screen has carried out the film of sided corona treatment) bonding with metal foil layer 14. Then, by will by substrate layer 11, adhesive linkage 13, corrosion-proof layer 15a, metal foil layer 14, The construction temperature that corrosion-proof layer 15b, sealing adhesive linkage 16 and sealant 17 are constituted is 40 DEG C atmosphere in place 6 days, thus carried out maturation process.Thus, electrical storage device has been made with exterior Component 10.
(comparative example 1-1)
In comparative example 1-1, in addition to substrate layer 11 is become nylon membrane A-1-2, with embodiment 1-1 Similarly make electrical storage device exterior member 10.
The evaluation ＞ of ＜ form depth
For in embodiment 1-1 and comparative example 1-1 make electrical storage device exterior member 10, use with Under method have rated the form depth that can carry out deep-draw molding.First, electrical storage device is used exterior structure Part 10 is arranged in shaped device in the way of making sealant 17 upward.By the molding of shaped device Depth-set is 5.0～7.5mm, each is spaced apart 0.5mm, room temperature be 23 DEG C, dew point temperature be Cold forming is carried out in the environment of-35 DEG C.Further, diel employs the length with 70mm × 80mm Square cross section, there is in bottom surface the punch radius (RP) of 1.00mm, in side, there is 1.00mm The diel of angle of attack radius (RCP).It addition, mouth die mould employs and has on peristome The mouth die mould of the mouth die radius (RD) of 1.00mm.While exterior member 10 being irradiated light while leading to Cross be visually confirmed to be the part having carried out cold forming with or without fracture and pin hole, obtained can fracture and pin hole The maximum of the form depth of deep-draw molding in the case of the most not occurring.Show the result in table 1.
The evaluation ＞ of ＜ adaptation
For in embodiment 1-1 and comparative example 1-1 make electrical storage device exterior member 10, use with Under method have rated the adaptation between substrate layer 11 and metal foil layer 14.First, by electrical storage device It is arranged in shaped device in the way of making sealant 17 upward by exterior member 10.Molding is filled The form depth put is set as 5mm, room temperature be 23 DEG C, dew point temperature for-35 DEG C in the environment of carry out Cold forming.Further, diel employ have 70mm × 80mm rectangular cross section, Bottom surface has the punch radius (RP) of 1.00mm, has the angle of attack radius (RCP) of 1.00mm in side Diel.It addition, mouth die mould employs the mouth die radius on peristome with 1.00mm (RD) mouth die mould.
It follows that the exterior member 10 through cold forming is put into equipped with 1M lithium lithium phosphate solution (molten Agent volume ratio=ethyl carbonate: dimethyl carbonate: dimethyl carbonate=1:1:1) 100mL of 30mL In the beaker of capacity.It follows that the beaker that will be equipped with exterior member 10 is enclosed in a pipeful of tank, by Place 2 hours under the temperature environment of 40 DEG C, so that exterior member 10 is exposed in electrolyte.Then, Exterior member 10 is taken out by the beaker in a pipeful of tank, puts into the baking oven of 110 DEG C, in temperature be In the environment of 60 DEG C and humidity are 95% or in the hot water of 50 DEG C.Then, after it is 1 week, 2 Zhou Hou, after 3 weeks and after 4 weeks, by being visually confirmed to be substrate layer 11 and the metal foil layer of exterior member 10 With or without stripping between 14, obtain and do not confirm there is stripping between substrate layer 11 and metal foil layer 14 The maximum (unit: week) of period.Based on its result, according to following evaluation criterion, to substrate layer Adaptation between 11 and metal foil layer 14 is evaluated.Show the result in table 1.
A: even if the most not confirming there is stripping.
B: the most do not confirm to have stripping, but there occurs stripping after 4 weeks.
C: the most do not confirm to have stripping, but there occurs stripping after 3 weeks.
D: do not had confirmation to have stripping after 1 week, but there occurs stripping after 2 weeks.
E: there occurs stripping after 1 week.
Table 1
Knowable to the result shown in table 1, make the exterior member that thickness is 15 μm of substrate layer 11 In, employ 95 DEG C of hot water shrinkages less than 5% and polyamide that 180 DEG C of percent thermal shrinkages are 4～16% Film is unsatisfactory for employing 180 DEG C of percent thermal shrinkages as the exterior member of embodiment 1-1 of substrate layer 11 The exterior member of the comparative example 1-1 stating the polyamide membrane of condition is compared, it is thus identified that can maintain adaptation While improve deep-draw mouldability.
(embodiment 1-2)
In embodiment 1-2, except forming anticorrosion instead of using polyphosphate sodium stabilisation cerium oxide sol Process layer 15a and 15b, and by being coated with by phenolic resin, fluorination on the two sides of metal foil layer 14 Chromium compound and phosphoric acid composition treatment fluid and form tunicle, be sintered, thus carry out chromate process And form corrosion-proof layer 15a and 15b, and substrate layer 11 is become beyond nylon membrane B-1-1, Electrical storage device exterior member 10 has been made in the same manner as embodiment 1-1.
(embodiment 1-3)
In embodiment 1-3, in addition to substrate layer 11 is become nylon membrane B-1-2, with embodiment 1-1 Similarly make electrical storage device exterior member 10.
(embodiment 1-4)
In embodiment 1-4, in addition to substrate layer 11 is become nylon membrane B-1-3, with embodiment 1-1 Similarly make electrical storage device exterior member 10.
(embodiment 1-5)
In embodiment 1-5, in addition to substrate layer 11 is become nylon membrane B-1-4, with embodiment 1-1 Similarly make electrical storage device exterior member 10.
(comparative example 1-2)
In comparative example 1-2, in addition to substrate layer 11 is become nylon membrane B-1-5, with embodiment 1-1 Similarly make electrical storage device exterior member 10.
(comparative example 1-3)
In comparative example 1-3, in addition to substrate layer 11 is become nylon membrane B-1-6, with embodiment 1-1 Similarly make electrical storage device exterior member 10.
(comparative example 1-4)
In comparative example 1-4, in addition to substrate layer 11 is become nylon membrane B-1-7, with embodiment 1-1 Similarly make electrical storage device exterior member 10.
The evaluation ＞ of ＜ form depth
For the electrical storage device exterior member made in embodiment 1-2～1-5 and comparative example 1-2～1-4 10, the test method that employing and the above embodiments 1-1 etc. are identical, for carrying out deep-draw molding Form depth is evaluated.Show the result in table 2.
The evaluation ＞ of ＜ adaptation
For the electrical storage device exterior member made in embodiment 1-2～1-5 and comparative example 1-2～1-4 10, the test method that employing and the above embodiments 1-1 etc. are identical, have rated substrate layer 11 and metal Adaptation between layers of foil 14.Show the result in table 2.
Table 2
Knowable to the result shown in table 2, about the exterior structure that the thickness making substrate layer 11 is 25 μm Part, employs 95 DEG C of hot water shrinkages less than 5% and polyamide that 180 DEG C of percent thermal shrinkages are 4～16% Film as embodiment 1-2 of substrate layer 11～the exterior member of 1-5 with employ 95 DEG C of hot water shrinkages and At least one of 180 DEG C of percent thermal shrinkages is unsatisfactory for comparative example 1-2's～1-4 of the polyamide membrane of above-mentioned condition Exterior member is compared, it is thus identified that can improve deep-draw mouldability while maintaining adaptation well.
(embodiment 1-6)
In embodiment 1-6, following change is carried out for embodiment 1-1.In embodiment 1-6, Substrate layer 11 is become nylon membrane C-1-1.It addition, sealing adhesive linkage 16 is by gluing as sealing Connect the maleic anhydride modified polypropylene (Mitsui Chemicals society system, trade name: ADMER) of the mother metal of layer 16 Extrude formation.Now, the thickness making sealing adhesive linkage 16 is 20 μm.It addition, replacement dry lamination Method, uses interlayer lamination, via sealing adhesive linkage 16 in corrosion-proof layer 15b at 180 DEG C Under bonding (adding thermo-compressed) as the polyolefin film that thickness is 60 μm of sealant 17 (to non-stretched The face sealing adhesive linkage 16 side of polypropylene screen has carried out the film of sided corona treatment).In embodiment 1-6, remove Carry out, beyond above-mentioned change, having made electrical storage device exterior member in the same manner as embodiment 1-1 10。
(embodiment 1-7)
In embodiment 1-7, in addition to substrate layer 11 is become nylon membrane C-1-2, with embodiment 1-6 Similarly make electrical storage device exterior member 10.
(embodiment 1-8)
In embodiment 1-8, in addition to substrate layer 11 is become nylon membrane C-1-3, with embodiment 1-6 Similarly make electrical storage device exterior member 10.
The evaluation ＞ of ＜ form depth
For the electrical storage device exterior member 10 made in embodiment 1-6～1-8, use with above-mentioned The test method that embodiment 1-1 etc. are identical, have rated the form depth that can carry out deep-draw molding.Will knot Fruit is shown in Table 3.
The evaluation ＞ of ＜ adaptation
For the electrical storage device exterior member 10 made in embodiment 1-6～1-8, use with above-mentioned The test method that embodiment 1-1 etc. are identical, have rated between substrate layer 11 and metal foil layer 14 is closely sealed Property.Show the result in table 3.
Table 3
Knowable to the result shown in table 3, about the exterior structure that the thickness making substrate layer 11 is 25 μm Part, employs 95 DEG C of hot water shrinkages less than 5% and polyamide that 180 DEG C of percent thermal shrinkages are 4～16% Film embodiment 1-6 as substrate layer 11～the exterior member of 1-8, even if using interlayer lamination to set In the case of having put sealing adhesive linkage 16, also confirm while maintaining adaptation, to improve deep-draw Mouldability.
(embodiment 1-9)
In embodiment 1-9, except replacing that the one side of substrate layer 11 is carried out sided corona treatment, and at base material Form easy bonding process layer 12 and substrate layer 11 is become Buddhist nun on the face of adhesive linkage 13 side of layer 11 Beyond dragon film D-1-1, make electrical storage device exterior member 10 in the same manner as embodiment 1-1.Easy to stick Connect process layer 12 by using streamline rubbing method so that dividing with solid and being calculated as on the one side of substrate layer 11 0.1g/m2Mode be coated with and become the smears of mother metal connecing and processing layer 12 easy to stick so that it is be dried, thus Define thickness and be about easy the to be bonding process layer 12 of 0.1 μm.
(comparative example 1-6)
In comparative example 1-6, in addition to substrate layer 11 is become nylon membrane D-1-2, with embodiment 1-9 Similarly make electrical storage device exterior member 10.
The evaluation ＞ of ＜ form depth
For in embodiment 1-9 and comparative example 1-6 make electrical storage device exterior member 10, use with The test method that the above embodiments 1-1 etc. are identical, have rated the form depth that can carry out deep-draw molding. Show the result in table 4.
The evaluation ＞ of ＜ adaptation
For in embodiment 1-9 and comparative example 1-6 make electrical storage device exterior member 10, use with The test method that the above embodiments 1-1 etc. are identical, have rated between substrate layer 11 and metal foil layer 14 Adaptation.Show the result in table 4.
Table 4
Knowable to the result shown in table 4, it is 25 μm about the thickness making substrate layer 11, is provided with easily The exterior member of bonding process layer 12, employs 95 DEG C of hot water shrinkages less than 5% and 180 DEG C of thermal contractions Rate be 4～16% polyamide membrane as embodiment 1-9 of substrate layer 11 exterior member with employ The exterior member of the comparative example 1-6 that 180 DEG C of percent thermal shrinkages are unsatisfactory for the polyamide membrane of above-mentioned condition is compared, Confirm while maintaining adaptation, to improve deep-draw mouldability.
(preparation of substrate layer)
As substrate layer 11, prepare to use the following poly-terephthaldehyde that biaxial stretching process manufactures simultaneously Acid glycol ester film A-2-1～A-2-2, B-2-1～B-2-7 and C-2-1～C-2-2.Described below each poly- The thickness of ethylene glycol terephthalate film, 95 DEG C of hot water shrinkages and 180 DEG C of percent thermal shrinkages.
A-2-1: thickness be 12 μm, 95 DEG C of hot water shrinkages be 3.5%, 180 DEG C of percent thermal shrinkages be 18.7%.
A-2-2: thickness be 12 μm, 95 DEG C of hot water shrinkages be 2.5%, 180 DEG C of percent thermal shrinkages be 6.0%.
B-2-1: thickness be 25 μm, 95 DEG C of hot water shrinkages be 2.8%, 180 DEG C of percent thermal shrinkages be 19.9%.
B-2-2: thickness be 25 μm, 95 DEG C of hot water shrinkages be 2.8%, 180 DEG C of percent thermal shrinkages be 19.9%.
B-2-3: thickness be 25 μm, 95 DEG C of hot water shrinkages be 3.3%, 180 DEG C of percent thermal shrinkages be 23.8%.
B-2-4: thickness be 25 μm, 95 DEG C of hot water shrinkages be 2.4%, 180 DEG C of percent thermal shrinkages be 11.2%.
B-2-5: thickness be 25 μm, 95 DEG C of hot water shrinkages be 2.6%, 180 DEG C of percent thermal shrinkages be 5.7%.
B-2-6: thickness be 25 μm, 95 DEG C of hot water shrinkages be 8.5%, 180 DEG C of percent thermal shrinkages be 19.0%.
B-2-7: thickness be 25 μm, 95 DEG C of hot water shrinkages be 6.0%, 180 DEG C of percent thermal shrinkages be 19.9%.
C-2-1: thickness be 25 μm, 95 DEG C of hot water shrinkages be 2.6%, 180 DEG C of percent thermal shrinkages be 18.4%.
C-2-2: thickness be 25 μm, 95 DEG C of hot water shrinkages be 3.1%, 180 DEG C of percent thermal shrinkages be 6.6%.
(preparation of easy bonding process layer formation smears)
As easy bonding process layer formation smears, it is prepared for the smears of following composition.
Smears: at the water-soluble polyester " ARON MELT PES-1000 " of Toagosei Co., Ltd In with 95/5/0.5 match ratio (mass ratio) add Nippon Polyurethane Industry Co., Ltd. self emulsifying Type polyisocyanate " AQUANATE 100 " and the ball of Nippon Shokubai Kagaku Kogyo Co., Ltd Shape silicon dioxide microparticle " SEAHOSTAR KE-P30 " (mean diameter is 0.3 μm), dilute with water.
(embodiment 2-1)
In embodiment 2-1, make electrical storage device exterior member 10 by following method.First, make For metal foil layer 14, prepare soft aluminium foil 8079 material (aluminum Co., Ltd. of Japan that thickness is 40 μm System).It follows that use distilled water conduct by gravure coating process coating on the two sides of metal foil layer 14 Solvent and to be adjusted to polyphosphate sodium stabilisation cerium oxide sol that solid point concentration is 10 mass % (anti- Corrosion treatmentCorrosion Science agent).Now, relative to cerium oxide 100 mass parts, making phosphoric acid is 10 mass parts.
It follows that make the polyphosphate sodium stabilisation cerium oxide sol of coating after drying, by burning successively Knot processes, and forms corrosion-proof layer 15a, at metal foil layer 14 in the one side of metal foil layer 14 Corrosion-proof layer 15b is formed on another side.Now, as sintering condition, making temperature is 150 DEG C, Making the process time is 30 seconds.
It follows that as substrate layer 11, use polyethylene terephthalate film A-2-1, to base material The one side of layer 11 has carried out sided corona treatment.
It follows that the opposition side with metal foil layer 14 of corrosion-proof layer 15a at metal foil layer 14 Face on, coating urethane adhesive as adhesive linkage 13.It follows that by dry lamination method, Via adhesive linkage 13, metal foil layer 14 is bonding with the face that the sided corona treatment of substrate layer 11 is crossed.Then, By will be by substrate layer 11, adhesive linkage 13, corrosion-proof layer 15a, metal foil layer 14 and anticorrosion Process in the atmosphere that construction temperature is 60 DEG C that layer 15b is constituted and place 6 days, thus carried out ripe Change processes.
It follows that on the face with the opposition side of metal foil layer 14 of corrosion-proof layer 15b, formed Sealing adhesive linkage 16.Now, sealing adhesive linkage 16 is by using as the mother sealing adhesive linkage 16 Formation extruded by the maleic anhydride modified polypropylene (Mitsui Chemicals society system, trade name: ADMER) of material. Now, the thickness making sealing adhesive linkage 16 is 20 μm.It follows that by interlayer lamination, via close Envelope adhesive linkage 16 is bonding at 180 DEG C (adding thermo-compressed) as sealing in corrosion-proof layer 15b The polyolefin film that thickness is 60 μm of layer 17 (seals adhesive linkage 16 side to un-stretched polypropylene film Face has carried out the film of sided corona treatment).Thus, electrical storage device exterior member 10 has been made.
(comparative example 2-1)
In comparative example 2-1, except substrate layer 11 being become polyethylene terephthalate film A-2-2 In addition, electrical storage device exterior member 10 has been made in the same manner as embodiment 2-1.
The evaluation ＞ of ＜ form depth
For in embodiment 2-1 and comparative example 2-1 make electrical storage device exterior member 10, use with Under method have rated the form depth that can carry out deep-draw molding.First, electrical storage device is used exterior structure Part 10 is arranged in shaped device in the way of making sealant 17 upward.By the molding of shaped device Depth-set is 4.5～7.5mm, each is spaced apart 0.5mm, room temperature be 23 DEG C, dew point temperature be Cold forming is carried out in the environment of-35 DEG C.Further, diel employs the length with 70mm × 80mm Square cross section, there is in bottom surface the punch radius (RP) of 1.00mm, in side, there is 1.00mm The diel of angle of attack radius (RCP).It addition, mouth die mould employs and has on peristome The mouth die mould of the mouth die radius (RD) of 1.00mm.While exterior member 10 being irradiated light while leading to Cross be visually confirmed to be the part having carried out cold forming with or without fracture and pin hole, obtained can fracture and pin hole The maximum of the form depth of deep-draw molding is carried out in the case of the most not occurring.Show the result in table 5. In table, at least one split and in pin hole is resolved in " ＜ 4.5 " expression under form depth 4.5mm.
The evaluation ＞ of ＜ adaptation
For in embodiment 2-1 and comparative example 2-1 make electrical storage device exterior member 10, use with Under method have rated the adaptation between substrate layer 11 and metal foil layer 14.First, by electrical storage device It is arranged in shaped device in the way of making sealant 17 upward by exterior member 10.Molding is filled The form depth put is set as 5mm, room temperature be 23 DEG C, dew point temperature for-35 DEG C in the environment of carry out Cold forming.Further, diel employ have 70mm × 80mm rectangular cross section, Bottom surface has the punch radius (RP) of 1.00mm, has the angle of attack radius (RCP) of 1.00mm in side Diel.It addition, mouth die mould employs the mouth die radius on peristome with 1.00mm (RD) mouth die mould.
It follows that the exterior member 10 through cold forming is put into equipped with 1M lithium lithium phosphate solution (molten Agent volume ratio=ethyl carbonate: dimethyl carbonate: dimethyl carbonate=1:1:1) 100mL of 30mL In the beaker of capacity.It follows that the beaker that will be equipped with exterior member 10 is enclosed in a pipeful of tank, by Place 2 hours under the temperature environment of 40 DEG C, so that exterior member 10 is exposed to electrolyte.Then, Beaker in a pipeful of tank takes out exterior member 10, puts into the baking oven of 110 DEG C, be 60 in temperature DEG C and humidity be 95% in the environment of or in the hot water of 50 DEG C.Then, after it is 1 week, 2 Zhou Hou, after 3 weeks, after 4 weeks and after 9 weeks, by be visually confirmed to be the substrate layer 11 of exterior member 10 with With or without stripping between metal foil layer 14, obtain and do not confirm between substrate layer 11 and metal foil layer 14 There is the maximum (unit: week) of the period of stripping.Based on its result, according to following evaluation criterion, Adaptation between substrate layer 11 and metal foil layer 14 is evaluated.Show the result in table 5. If the evaluation of more than B, then it may be said that the adaptation between substrate layer 11 and metal foil layer 14 is good.
A: even if the most not confirming there is stripping after 9 weeks.
Do not have confirmation to have stripping after B:4 week, but there occurs stripping after 9 weeks.
Do not have confirmation to have stripping after C:3 week, but there occurs stripping after 4 weeks.
Do not have confirmation to have stripping after D:2 week, but there occurs stripping after 3 weeks.
Do not have confirmation to have stripping after E:1 week, but there occurs stripping after 2 weeks.
F:1 there occurs stripping after week.
Table 5
Knowable to the result shown in table 5, about the exterior structure that the thickness making substrate layer 11 is 12 μm Part, employs 95 DEG C of hot water shrinkages less than 5% and polyester film that 180 DEG C of percent thermal shrinkages are 10～25% Exterior member as embodiment 2-1 of substrate layer 11 is unsatisfactory for above-mentioned with employing 180 DEG C of percent thermal shrinkages The exterior member of the comparative example 2-1 of the polyester film of condition is compared, it is thus identified that can maintain the same of adaptation Shi Tigao deep-draw mouldability.
(embodiment 2-2)
In embodiment 2-2, following change is carried out for embodiment 2-1.In embodiment 2-2, make For sealing adhesive linkage 16, it is coated with in the mixed solvent being toluene and hexahydrotoluene the acid dissolved and changes Property polyolefin has coordinated the urethane adhesive of polyisocyanates.It addition, replace interlayer lamination, And use dry lamination method, it is 40 μm via sealing adhesive linkage 16 using the thickness as sealant 17 Polyolefin film (face that un-stretched polypropylene film seals adhesive linkage 16 side has carried out the film of sided corona treatment) Bonding with metal foil layer 14.Then, by will be by substrate layer 11, adhesive linkage 13, corrosion-proof layer 15a, metal foil layer 14, corrosion-proof layer 15b, sealing adhesive linkage 16 and sealant 17 are constituted Construction temperature is to place 6 days in the atmosphere of 40 DEG C, thus has carried out maturation process.Embodiment 2-2 In, carry out beyond above-mentioned change, made the exterior structure of electrical storage device in the same manner as embodiment 2-1 Part 10.
The evaluation ＞ of ＜ form depth
For the electrical storage device exterior member 10 made in embodiment 2-2, use and the above embodiments The test method that 2-1 etc. are identical, have rated the form depth that can carry out deep-draw molding.Show the result in In table 6.
The evaluation ＞ of ＜ adaptation
For the electrical storage device exterior member 10 made in embodiment 2-2, use and the above embodiments The test method that 2-1 etc. are identical, have rated the adaptation between substrate layer 11 and metal foil layer 14.Will Result is shown in Table 6.
Table 6
Understand like that from the result shown in table 6, be 12 μm about the thickness making substrate layer 11 Exterior member, less than 5% and 180 DEG C of percent thermal shrinkages are 10～25% to employ 95 DEG C of hot water shrinkages Polyester film is as the exterior member of embodiment 2-2 of substrate layer 11, even if using dry lamination method to set In the case of having put sealing adhesive linkage 16, it is thus identified that also be able to while maintaining adaptation improve deep-draw Mouldability.
(embodiment 2-3)
In embodiment 2-3, except forming anticorrosion instead of using polyphosphate sodium stabilisation cerium oxide sol Process layer 15a and 15b and pass through to be coated with by phenolic resin, fluorination on the two sides of metal foil layer 14 Chromium compound and phosphoric acid composition treatment fluid and form tunicle, be sintered, thus carry out chromate process Form corrosion-proof layer 15a and 15b, and substrate layer 11 is become poly terephthalic acid second two Beyond alcohol ester film B-2-1, make electrical storage device exterior member 10 in the same manner as embodiment 2-1.
(embodiment 2-4)
In embodiment 2-4, except substrate layer 11 being become polyethylene terephthalate film B-2-2 In addition, electrical storage device exterior member 10 has been made in the same manner as embodiment 2-1.
(embodiment 2-5)
In embodiment 2-5, except substrate layer 11 being become polyethylene terephthalate film B-2-3 In addition, electrical storage device exterior member 10 has been made in the same manner as embodiment 2-1.
(embodiment 2-6)
In embodiment 2-6, except substrate layer 11 being become polyethylene terephthalate film B-2-4 In addition, electrical storage device exterior member 10 has been made in the same manner as embodiment 2-1.
(comparative example 2-2)
In comparative example 2-2, except substrate layer 11 being become polyethylene terephthalate film B-2-5 In addition, electrical storage device exterior member 10 has been made in the same manner as embodiment 2-1.
(comparative example 2-3)
In comparative example 2-3, except substrate layer 11 being become polyethylene terephthalate film B-2-6 In addition, electrical storage device exterior member 10 has been made in the same manner as embodiment 2-1.
(comparative example 2-4)
In comparative example 2-4, except substrate layer 11 being become polyethylene terephthalate film B-2-7 In addition, electrical storage device exterior member 10 has been made in the same manner as embodiment 2-1.
The evaluation ＞ of ＜ form depth
For the electrical storage device exterior member made in embodiment 2-3～2-6 and comparative example 2-2～2-4 10, the test method that employing and the above embodiments 2-1 etc. are identical, have rated and can carry out deep-draw molding Form depth.Show the result in table 7.
The evaluation ＞ of ＜ adaptation
For the electrical storage device exterior member made in embodiment 2-3～2-6 and comparative example 2-2～2-4 10, the test method that employing and the above embodiments 2-1 etc. are identical, have rated substrate layer 11 and metal Adaptation between layers of foil 14.Show the result in table 7.
Table 7
Knowable to the result shown in table 7, about the exterior structure that the thickness making substrate layer 11 is 25 μm Part, employs 95 DEG C of hot water shrinkages less than 5% and polyester film that 180 DEG C of percent thermal shrinkages are 10～25% As embodiment 2-3 of substrate layer 11～the exterior member of 2-6 with employ 95 DEG C of hot water shrinkages and At least one of 180 DEG C of percent thermal shrinkages is unsatisfactory for outside comparative example 2-2～2-4 of the polyester film of above-mentioned condition Dress component is compared, it is thus identified that can improve deep-draw mouldability while maintaining adaptation.
(embodiment 2-7)
In embodiment 2-7, replace the one side of substrate layer 11 is carried out sided corona treatment and at substrate layer 11 Form easy bonding process layer 12 on the face of adhesive linkage 13 side, and it is poly-to benzene two that substrate layer 11 is become Beyond formic acid glycol ester film C-2-1, make the exterior structure of electrical storage device in the same manner as embodiment 2-1 Part 10.Easy bonding process layer 12 by use streamline rubbing method on the one side of substrate layer 11 so that 0.1g/m is become in terms of solid is divided2Mode be coated with and become the smears of mother metal connecing and processing layer 12 easy to stick, Make it be dried, thus define thickness and be about easy the to be bonding process layer 12 of 0.1 μm.
(comparative example 2-5)
In comparative example 2-5, except substrate layer 11 being become polyethylene terephthalate film C-2-2 In addition, electrical storage device exterior member 10 has been made in the same manner as embodiment 2-7.
The evaluation ＞ of ＜ form depth
For in embodiment 2-7 and comparative example 2-5 make electrical storage device exterior member 10, use with The test method that the above embodiments 2-1 etc. are identical, have rated the form depth that can carry out deep-draw molding. Show the result in table 8.
The evaluation ＞ of ＜ adaptation
For in embodiment 2-7 and comparative example 2-5 make electrical storage device exterior member 10, use with The test method that the above embodiments 2-1 etc. are identical, have rated between substrate layer 11 and metal foil layer 14 Adaptation.Show the result in table 8.
Table 8
Knowable to the result shown in table 8, it is 25 μm about the thickness making substrate layer 11, is provided with easily The exterior member of bonding process layer 12, employs 95 DEG C of hot water shrinkages less than 5% and 180 DEG C of thermal contractions Rate be 10～25% polyester film as embodiment 2-7 of substrate layer 11 exterior member with employ 180 The exterior member of the comparative example 2-5 that DEG C percent thermal shrinkage is unsatisfactory for the polyester film of above-mentioned condition is compared, it is thus identified that Deep-draw mouldability can be improved while maintaining adaptation.

Claims (4)

1. an electrical storage device exterior member, it is characterised in that it has the structure stacked gradually to major general's substrate layer, adhesive linkage, metal foil layer, corrosion-proof layer, sealing adhesive linkage and sealant.
Electrical storage device exterior member the most according to claim 1, it is characterized in that, described substrate layer be by 95 DEG C of hot water shrinkages less than 5% and 180 DEG C of percent thermal shrinkages be 4～the layer that constitutes of polyamide membrane of 16% or by 95 DEG C of hot water shrinkages less than 5% and the layer that constitutes of polyester film that 180 DEG C of percent thermal shrinkages are 10～25%.
Electrical storage device exterior member the most according to claim 1 and 2, it is characterised in that be also equipped with between described substrate layer with described adhesive linkage easy the to be bonding process layer arranged.
4. an electrical storage device, it is characterised in that it possesses: comprise the battery unit of electrode；The lead-in wire extended out from described electrode；With the container of the described battery unit of receiving, wherein, the electrical storage device exterior member described in the described container any one by claims 1 to 3 is formed in the way of making described sealant become inner side.
CN201620159207.8U 2015-03-03 2016-03-02 Power storage device is with adorning component outward and having used this outer power storage device who adorns component Active CN205631608U (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015041274A JP6819029B2 (en) 2015-03-03 2015-03-03 Exterior material for power storage device and power storage device using it
JP2015-041274 2015-03-03
JP2015041271A JP6596844B2 (en) 2015-03-03 2015-03-03 Power storage device exterior material and power storage device using the same
JP2015-041271 2015-03-03

Publications (1)

Publication Number Publication Date
CN205631608U true CN205631608U (en) 2016-10-12

Family

ID=56849374

Family Applications (3)

Application Number Title Priority Date Filing Date
CN201680012536.2A Pending CN107408642A (en) 2015-03-03 2016-03-02 Electrical storage device is with encapsulating material and uses its electrical storage device
CN201620159207.8U Active CN205631608U (en) 2015-03-03 2016-03-02 Power storage device is with adorning component outward and having used this outer power storage device who adorns component
CN202210322936.0A Pending CN114696014A (en) 2015-03-03 2016-03-02 Packaging material for power storage device, and power storage device using same

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201680012536.2A Pending CN107408642A (en) 2015-03-03 2016-03-02 Electrical storage device is with encapsulating material and uses its electrical storage device

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN202210322936.0A Pending CN114696014A (en) 2015-03-03 2016-03-02 Packaging material for power storage device, and power storage device using same

Country Status (5)

Country Link
US (1) US10693111B2 (en)
EP (1) EP3267506B1 (en)
KR (1) KR102662941B1 (en)
CN (3) CN107408642A (en)
WO (1) WO2016140256A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108179407A (en) * 2017-12-19 2018-06-19 乐凯胶片股份有限公司 A kind of soft package lithium battery passivating solution and its packaging material
CN109844984A (en) * 2016-10-20 2019-06-04 凸版印刷株式会社 Electrical storage device encapsulating material and the electrical storage device for using it
CN109963712A (en) * 2016-12-28 2019-07-02 日本瑞翁株式会社 Film

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6862084B2 (en) * 2015-10-07 2021-04-21 昭和電工パッケージング株式会社 Packaging materials, cases and power storage devices
JP6037070B1 (en) * 2016-02-22 2016-11-30 大日本印刷株式会社 Dimming cell
KR20170139303A (en) * 2016-06-09 2017-12-19 주식회사 엘지화학 Secondary Battery
JP2018055976A (en) * 2016-09-29 2018-04-05 昭和電工パッケージング株式会社 Packaging material and method for manufacturing the same
WO2018174056A1 (en) * 2017-03-21 2018-09-27 大日本印刷株式会社 Packaging material for batteries, method for producing same, polybutylene terephthalate film for packaging material for batteries, and battery
JP6943045B2 (en) * 2017-07-10 2021-09-29 凸版印刷株式会社 Exterior material for power storage device and power storage device using it
WO2019013099A1 (en) 2017-07-10 2019-01-17 凸版印刷株式会社 Outer package material for electricity storage devices, and electricity storage device using same
JP7033414B2 (en) * 2017-09-14 2022-03-10 昭和電工パッケージング株式会社 Packaging materials for molding, exterior cases for power storage devices and power storage devices
WO2021033708A1 (en) * 2019-08-20 2021-02-25 大日本印刷株式会社 Quality control method in molding process of power storage device exterior material, manufacturing method for power storage device, power storage device exterior material, and power storage device
US10849235B1 (en) * 2020-05-20 2020-11-24 Tactotek Oy Method of manufacture of a structure and structure
CN113745718A (en) * 2020-05-29 2021-12-03 昭和电工包装株式会社 Laminate for outer packaging material of electricity storage device
KR102522216B1 (en) * 2020-09-04 2023-04-18 율촌화학 주식회사 Primer layer composition, secondary battery pouch film using the same, and method for manufacturing the same

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100562468B1 (en) * 2000-12-26 2006-03-17 주식회사 코오롱 Manufacturing method of Polyamide film
EP1315219B1 (en) * 2001-06-20 2010-09-01 Dai Nippon Printing Co., Ltd. Battery packing material
JP5519895B2 (en) * 2005-05-27 2014-06-11 昭和電工パッケージング株式会社 Battery case packaging and battery case
GB0602678D0 (en) * 2006-02-09 2006-03-22 Dupont Teijin Films Us Ltd Polyester film and manufacturing process
TWI501446B (en) * 2010-09-08 2015-09-21 Toppan Printing Co Ltd Exterior material for lithium-ion battery
TWI511351B (en) * 2010-10-14 2015-12-01 Toppan Printing Co Ltd Lithium-ion battery exterior materials
HUE037546T2 (en) * 2010-12-24 2018-09-28 Toray Industries Polyester film and laminate using same
JP5966611B2 (en) * 2011-05-24 2016-08-10 東レ株式会社 Laminated body
EP2779266B1 (en) * 2011-11-07 2017-08-02 Toppan Printing Co., Ltd. Outer-covering material for electricity-storage device
KR102021325B1 (en) * 2011-11-07 2019-09-16 도판 인사츠 가부시키가이샤 Outer-covering material for electricity-storage device
JP5948796B2 (en) 2011-11-07 2016-07-06 凸版印刷株式会社 Exterior materials for lithium-ion batteries
JP5942385B2 (en) 2011-11-07 2016-06-29 凸版印刷株式会社 Power storage device exterior materials
EP2878616A4 (en) * 2012-07-24 2016-03-30 Unitika Ltd Polyester film for cold forming and method for producing same
JP5954084B2 (en) * 2012-09-28 2016-07-20 東レ株式会社 Laminated body
JP2014069383A (en) * 2012-09-28 2014-04-21 Toray Ind Inc Laminate
JP6469356B2 (en) * 2013-07-29 2019-02-13 昭和電工パッケージング株式会社 Battery case

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109844984A (en) * 2016-10-20 2019-06-04 凸版印刷株式会社 Electrical storage device encapsulating material and the electrical storage device for using it
CN109963712A (en) * 2016-12-28 2019-07-02 日本瑞翁株式会社 Film
CN108179407A (en) * 2017-12-19 2018-06-19 乐凯胶片股份有限公司 A kind of soft package lithium battery passivating solution and its packaging material

Also Published As

Publication number Publication date
US10693111B2 (en) 2020-06-23
WO2016140256A1 (en) 2016-09-09
EP3267506A4 (en) 2018-11-21
US20170365825A1 (en) 2017-12-21
KR20170125047A (en) 2017-11-13
EP3267506A1 (en) 2018-01-10
CN107408642A (en) 2017-11-28
EP3267506B1 (en) 2023-11-01
CN114696014A (en) 2022-07-01
KR102662941B1 (en) 2024-05-03

Similar Documents

Publication Publication Date Title
CN205631608U (en) Power storage device is with adorning component outward and having used this outer power storage device who adorns component
CN108604645A (en) The manufacturing method of electrical storage device encapsulating material and electrical storage device encapsulating material
CN109314194B (en) Sealing material for electricity storage device
TWI684301B (en) Exterior materials for power storage devices
CN103155207B (en) Exterior material for lithium ion battery
CN103518272B (en) Cladding for lithium ion cell, lithium ion cell, and method for producing lithium ion cell
CN103918099B (en) Electrical storage device housing material
US10468639B2 (en) Lithium battery packaging material
CN108140751A (en) The manufacturing method of electrical storage device encapsulating material and electrical storage device encapsulating material
CN106252533A (en) Electrical storage device exterior member
CN105210209B (en) Lithium ion battery encapsulating material
CN110998895B (en) Outer packaging material for power storage device
TW200915639A (en) Packing material for lithium cell and production method thereof
CN108604649A (en) The manufacturing method of electrical storage device encapsulating material and electrical storage device encapsulating material
CN106104843A (en) Lithium battery encapsulating material
CN105849932A (en) Exterior material for lithium cell
CN206584964U (en) Electrical storage device exterior member and the electrical storage device for having used it
CN115764090A (en) Sealing material for electricity storage device
CN109643770A (en) Electrical storage device housing material
JP5278636B2 (en) Lithium battery packaging material
CN108140749B (en) Packaging material for power storage device, and power storage device using same
JP2019102262A (en) Aluminum plastic film packaging material for lithium battery for extending service life
CN109844984A (en) Electrical storage device encapsulating material and the electrical storage device for using it
CN108886113A (en) The manufacturing method of electrical storage device encapsulating material and electrical storage device encapsulating material
CN110832662B (en) Material for packaging electricity storage device and electricity storage device using same

Legal Events

Date Code Title Description
C14 Grant of patent or utility model
GR01 Patent grant